The present invention relates generally to ion optics for mass spectrometers, and more particularly to a device for confining and focusing ions at atmospheric pressure and at moderate vacuum conditions and to ion source apparatuses using the device.
A fundamental challenge faced by designers of mass spectrometers is the efficient transport of ions from the ion source to the mass analyzer, particularly through atmospheric or low vacuum regions where ion motion is substantially influenced by interaction with background gas molecules. While electrostatic optics are commonly employed in these regions of commercially available mass spectrometer instruments for ion focusing, it is known that the effectiveness of such devices is limited due to the large numbers of collisions experienced by the ions. Consequently, ion transport losses tend to be high, which has a significant adverse impact on the instrument's overall sensitivity.
Due to the differences in pressure between the ionization chamber 14 and the intermediate-vacuum chamber 18 (
The analyte ions exit the outlet end of ion transfer tube 16 as a free jet expansion and travel through an ion channel 41 defined within the interior of ion transport device 40. As discussed in further detail in U.S. Pat. No. 7,781,728, the entire disclosure of which is incorporated herein by reference, radial confinement and focusing of ions within ion channel 41 are achieved by application of oscillatory voltages to apertured electrodes 44 of ion transport device 40. As is further discussed in U.S. Pat. No. 7,781,728, transport of ions along ion channel 41 to the device exit may be facilitated by generating a longitudinal DC field and/or by tailoring the flow of the background gas in which the ions are entrained. Ions leave the ion transport device 40 as a narrowly focused beam and are directed through aperture 22 of extraction lens 29 into the second intermediate pressure chamber 25.
Subsequently, the ions pass thereafter through ion optical elements 20, 31 and 24 and are delivered through aperture 27 to a mass analyzer 28 located within chamber 26. The ion optical assemblies or lenses 20, 24 may comprise transfer elements, such as, for instance a multipole ion guide. The mass analyzer 28 comprises one or more detectors 30 whose output can be displayed as a mass spectrum. As depicted in
The reader is referred to U.S. Pat. No. 7,781,728 for more details of the ion transport device 40. Briefly, the ion transport device 40 is formed from a plurality of generally planar electrodes 44 arranged in longitudinally spaced-apart relation (as used herein, the term “longitudinally” denotes the axis defined by the overall movement of ions along ion channel 41). Devices of this general construction are sometimes referred to in the mass spectrometry art as “stacked-ring” ion guides. Each electrode 44 is adapted with an aperture through which ions may pass. The apertures collectively define an ion channel 41, which may be straight or curved, depending on the lateral alignment of the apertures. To improve manufacturability and reduce cost, all of the electrodes 44 may have identically sized apertures. An oscillatory (e.g., radio-frequency) voltage source applies oscillatory voltages to electrodes 44 to thereby generate a field that radially confines ions within ion channel 41. In order to create a tapered field that focuses ions to a narrow beam near the exit of the ion transport device 40, the inter-electrode spacing or the oscillatory voltage amplitude is increased in the direction of ion travel.
The electrodes 44 of the ion transport device 40 may be divided into a plurality of first electrodes interleaved with a plurality of second electrodes, with the first electrodes receiving an oscillatory voltage that is opposite in phase with respect to the oscillatory voltage applied to the second electrodes. Further, a longitudinal DC field may be created within the ion channel 41 by providing a DC voltage source (not illustrated) that applies a set of DC voltages to electrodes 44 in order to assist in propelling ions through the ion transport device 40.
Ion funnel and stacked ring ion guide apparatuses all perform their intended functions adequately. Nonetheless, the use of these prior apparatuses does present some difficulties. First, it is difficult to completely block the “line-of-sight” through such apparatuses for the purpose of preventing neutral molecules from traveling to down-stream mass spectrometer components (including the detector) where they may cause undesirable contamination and spurious detector noise. Secondly, since such apparatuses comprise multiple electrodes, proper alignment of all the components is time consuming and subject to later disruption. Thirdly, for the same reason, such apparatuses are difficult to clean once they do become contaminated. Fourthly, the provision of many parallel electrode plates in these conventional apparatuses produces a naturally high capacitance which may draw high RF power.
Radio Frequency (RF) ion carpets are an alternative type of focusing ion guide. Such RF ion carpets have previously been used in high energy physics experiments, but have not been seen for analytical applications. For example, Takamine et al. (“Space-charge effects in the catcher gas cell of a RF ion guide,” Review of Scientific Instruments, 76[10], pp. 103503-103503-6, 2005) and Schwarz (“RF ion carpets: The electric field, the effective potential, operational parameters and an analysis of stability,” International Journal of Mass Spectrometry, 299[2-3], pp. 71-77, 2011) have described the use of ion carpets for the capture of high energy particles in high energy physics experiments. The ion carpet apparatus described by Takamine et al. consists of distinct inner and outer regions. The inner region includes 160 concentric ring electrodes to which both RF voltages and DC potentials are applied, the inner-region ring electrodes being included within a diameter of 110 mm and having equal widths of approximately 0.14 mm with 0.14 mm separations between electrodes. The outer region, occupying radii between 55-140 mm, consists of 85 additional equal-width concentric ring electrodes separated by 0.2 mm to which only DC potentials and no RF fields are applied, each such outer-region ring electrode being approximately 0.8 mm wide. Such ion carpet devices should be suitable for use in atmospheric pressure ionization sources used in mass spectrometers and ion mobility spectrometers, but, to date, have not been employed for these analytical applications.
The previously described RF ion carpets have been designed with equally sized and spaced electrodes. Such a design produces a restoring force near the surface of the RF ion carpet that is essentially constant. Such a design presents some problems for mass spectrometry and ion mobility spectrometry applications in that, for spectrometry applications, one would normally like a strong restoring force to initially capture and control the ions, and then a weak restoring force near the center, so that ions can be more easily extracted for transfer to optics further down stream in the instrument. Accordingly, there is a need in the art of analytical ion spectrometry—including mass spectrometry and ion mobility spectrometry—for anew type of ion guide apparatus that it is relatively simple to construct, is easy to clean, can easily provide a complete blockage of line of site, thereby reducing noise at the detector and eliminating contamination concerns, provides a large acceptance aperture than can easily collect ions from multiple sources and that has a lower capacitance and RF usage than an ion funnel or SRIG with an equivalent number of plates. The present invention addresses such a need.
The inventors have realized that the variable restoring force required to use an RF ion carpet in analytical applications may be achieved by varying the size and spacing of the electrodes on the surface of the ion carpet. A preferred design may use larger electrodes towards the outer edges, to provide a strong repulsive force and initial capture of ions emerging from the atmospheric pressure expansion. Towards the center of the device, smaller electrodes may be used to allow the ions to approach closer to the surface, which would ease the eventual extraction. This variable electrode size and spacing also provides a natural way to increase the DC drag force towards the center while still using a linear voltage divider chain. Accordingly, an ion carpet with progressively sized and spaced electrodes is described which provides a natural way to reduce the repulsive threes near the exit orifice.
In accordance with one aspect of the invention, an ion transport apparatus for a mass spectrometer or an ion mobility spectrometer comprises: (a) a plurality of strip electrodes disposed in a series on a flat substrate; (b) an ion outlet aperture in the substrate disposed adjacent to a first one of the plurality of strip electrodes; (c) a cage electrode at least partially enclosing the plurality of strip electrodes and the ion outlet aperture; (d) extraction electrode disposed adjacent to the ion outlet aperture; (e) a radio frequency (RF) voltage generator operable to supply an oscillatory RF voltage to each of the plurality of strip electrodes such that an RF phase difference exists between each pair of adjacent electrodes; and (f) at least one DC voltage source operable to supply a first DC voltage to the cage electrode, a second DC voltage to the extraction electrode and a respective DC bias voltage to each of the plurality of electrodes, wherein each strip electrode comprises a respective width such that the electrode strip widths of a series of the plurality of electrodes progressively increase away from the first one of the plurality of electrodes.
In accordance with another aspect of the invention, a multiple ion source system for a mass spectrometer or an ion mobility spectrometer comprising: (a) an ion transport apparatus comprising: (i) a plurality of concentrically disposed strip electrodes on a flat substrate, each strip electrode comprising a respective width such that the electrode strip widths of a series of the plurality of strip electrodes progressively increase away from an innermost one of the plurality of electrodes; (ii) an ion outlet aperture in the substrate disposed adjacent to an innermost one of the plurality of strip electrodes; (iii) a cage electrode at least partially enclosing the plurality of strip electrodes and the ion outlet aperture; (iv) an ion transfer tube comprising an extraction electrode disposed adjacent to the ion outlet aperture; (v) a radio frequency (RF) voltage generator operable to supply an oscillatory RF voltage to each of the plurality of strip electrodes such that an RF phase difference exists between each pair of adjacent electrodes; and (vi) at least one DC voltage source operable to supply a first DC voltage to the cage electrode, a second DC voltage to the extraction electrode and a respective DC bias voltage to each of the plurality of electrodes; and (b) a plurality of ion sources circumferentially disposed about the plurality of concentrically disposed strip electrodes such that, in operation of each respective ion source, ions are emitted in the direction of at least a portion of the plurality of strip electrodes.
The above noted and various other aspects of the present invention will become apparent from the following description which is given by way of non-limiting example only and with reference to the accompanying drawings, not drawn to scale, in which:
The following description is presented to enable any person skilled in the art to make and use the invention, and is provided in the context of a particular application and its requirements. Various modifications to the described embodiments will be readily apparent to those skilled in the art and the generic principles herein may be applied to other embodiments. Thus, the present invention is not intended to be limited to the embodiments and examples shown but is to be accorded the widest possible scope in accordance with the features and principles shown and described. The particular features and advantages of the invention will become more apparent with reference to the appended
In operation of the RF ion carpet apparatus 50, an RF voltage generator (not shown in
The overall locus of ion pathways within the apparatus 50, as calculated according to the SIMION® simulation, as described above, is indicated by ion cloud 56. The simulations show high efficiency transfer of ions from the edge of the device to the central outlet aperture 51. An order of magnitude in mass is easily transferred without any variation in conditions. As can be seen in
The one-dimensional ion trajectory simulation whose results are indicated in
The cage electrode 77 (
The configuration shown in
The ion carpet apparatus 250, which may comprise, for example, the apparatus 70 shown in
The ion carpet apparatuses as described herein are expected to have several benefits over current high pressure RF devices like the SRIG and ion funnel. First, it is very simple to provide a complete blockage of line of site, thus reducing noise at the detector and eliminating concern about contamination of the instrument further down stream. Second, since the design is typically flat, apparatuses in accordance with the present teachings are relatively simple to construct. Third, the larger acceptance aperture of apparatuses in accordance with the present teachings can easily collect ions from multiple sources. Fourth, these apparatuses are very easy to clean. Fifth, the capacitance should be lower than a SRIG with an equivalent number of plates, and therefore should these novel apparatuses should use less RF power.
Improved ion collection, focusing, and transfer devices for on spectrometers used in analytical applications have been described. The novel devices are based on the concept of an ion carpet having concentric electrodes comprising electrode widths which progressively decrease from edge to center. The discussion included in this application is intended to serve as a basic description. Although the present invention has been described in accordance with the various embodiments shown and described, one of ordinary skill in the art will readily recognize that there could be variations to the embodiments or combinations of features in the various illustrated embodiments and those variations or combinations of features would be within the spirit and scope of the present invention. The reader should thus be aware that the specific discussion may not explicitly describe all embodiments possible; many alternatives are implicit. Accordingly, many modifications may be made by one of ordinary skill in the art without departing from the scope and essence of the invention. Neither the description nor the terminology is intended to limit the scope of the invention—the invention is defined only by the claims. Any patents, patent applications or other publications mentioned herein are hereby explicitly incorporated herein by reference in their respective entirety.
This application claims the priority benefit under 35 U.S.C. §119(e) of U.S. Provisional Application for Patent Ser. No. 61/679,501 entitled, “Ion Carpet for Mass Spectrometry Having Progressive Electrodes” filed Aug. 3, 2012, said provisional application incorporated by reference herein in its entirety for all purposes.
Number | Name | Date | Kind |
---|---|---|---|
3081020 | Rostas | Mar 1963 | A |
5248883 | Brewer et al. | Sep 1993 | A |
5302827 | Foley | Apr 1994 | A |
5572035 | Franzen | Nov 1996 | A |
6107628 | Smith et al. | Aug 2000 | A |
6180942 | Tracy et al. | Jan 2001 | B1 |
6583408 | Smith et al. | Jun 2003 | B2 |
6683301 | Whitehouse et al. | Jan 2004 | B2 |
8299443 | Shvartsburg et al. | Oct 2012 | B1 |
20100148062 | Wollnik et al. | Jun 2010 | A1 |
20130120894 | van Amerom et al. | May 2013 | A1 |
20130175440 | Perelman et al. | Jul 2013 | A1 |
Entry |
---|
Takamine et al., “Space-charge effects in the catcher gas cell of a rf ion guide,” Review of Scientific Instruments 76, 103503 (2005), pp. 1-6. |
S. Schwarz, “RF Ion Carpets, The electric field, the effective potential, operational parameters and an analysis of stability,” International Journal of Mass Spectrometry 299 (2011), pp. 71-77. |
Number | Date | Country | |
---|---|---|---|
20140034828 A1 | Feb 2014 | US |
Number | Date | Country | |
---|---|---|---|
61679501 | Aug 2012 | US |