The present disclosure relates to apparatuses, systems, and methods for performing mass spectrometric analysis using ion traps. More particularly, the present disclosure relates to apparatuses, systems, and methods for performing mass spectrometric analysis using cylindrical ion traps having a radial opening or openings in the ring electrode to improve capture efficiency and/or ionization efficiency.
An ion trap can be used to perform mass spectrometric chemical analysis, in which gaseous ions are filtered according to their mass-to-charge (m/z) ratio. The ion trap can dynamically trap ions from a measurement sample using dynamic electric fields generated by one or more driving signals. The ions can be selectively ejected according to their m/z ratio by changing the characteristics of the electric field. Relative abundance of different ionic species can be measured by scanning the characteristics of the electric field and detecting the ejected ions.
A typical mass spectrometer comprises an ionization source to generate ions from a measurement sample, an ion trap, which may be configured to receive ions and to separate ions in space and/or time, an ion detector to collect filtered/separated ions and measure their abundance, a vacuum system, and power source. Traditionally, to effect trapping of ions, buffer gas (or referred to as cooling gas or damping gas, usually helium) may be added to slow the ions down so that the ion trap can capture them and keep them in the trap. The buffer gas may also be inherently supplied with the sample, for example ambient air. Without the buffer gas, the ions may not be cooled sufficiently to be trapped by the electric field contained within the trap.
Recently, there has been a growing interest in miniaturized mass spectrometers. Miniature (or even portable) analyzers are especially useful in applications such as the detection of chemical warfare agents in combat, detection of pollutants in the field, detection of explosives at airport security checkpoints, etc. The portability of such miniature analyzers may be limited if the effect of cooling ions using a buffer gas is used to trap ions. For example, if an external gas tank has to be included, the overall system may be too large, heavy, or complex for field use. As well, the use of a buffer gas to cool ions may increase the gas load on the system such that pumping requirements are increased beyond what would be practical for a portable instrument. On the other hand, without sufficient buffer gas pressure, the ion capture efficiency may be too low. However, if the buffer gas pressure increases, resolution may suffer, especially when using buffer gasses of higher molecular weight.
Alternate architectures, such as quadrupole filter and time-of-flight mass spectrometers may exist that are more adapted to external ionization, however, these architectures do not lend themselves to miniaturization as well as ion traps. However, ions traps may not be suited to external ionization techniques because the distance over which ions are required to be cooled and trapped is relatively small compared to these architectures.
In addition, it is generally difficult for existing systems (e.g., cylindrical traps) to capture external ions due to potential energy and non-zero kinetic energy at the point of entry.
Therefore, it is desirable to develop ion trap systems and corresponding analyzing methods for performing mass spectrometric analysis with improved capture efficiency yet using a minimum amount of buffer gas pressure to cool the ions sufficiently.
Some disclosed embodiments may involve systems or apparatuses for performing mass analysis. One such system or apparatus may comprise an ion trap. The ion trap may comprise a first end cap having a first aperture and a second end cap having a second aperture, wherein the first aperture and the second aperture may define an ejection axis. The ion trap device may also comprise a ring electrode substantially coaxially aligned between the first and second end caps. The ring electrode may include an opening extending along a radial direction of the ring electrode, wherein the radial direction is substantially perpendicular to the ejection axis.
Some disclosed embodiments may involve methods for performing mass analysis. One such method may comprise ionizing a sample in an ion trap through an opening separating at least part of first and second ring sections of the ion trap, wherein the first and second ring sections are configured to be substantially coaxially aligned along an ejection axis; and detecting ions ejected though an aperture on an end cap of the ion trap.
Another such method may comprise ionizing a sample in an ion trap through an opening of a ring electrode, the opening extending along a radial direction of the ring electrode, wherein the radial direction is substantially perpendicular to an ejection axis of the ion trap; and detecting ions ejected though an aperture on an end cap of the ion trap.
Another such method may comprise receiving ions of a sample into an ion trap through an opening separating at least part of first and second ring sections of the ion trap, wherein the first and second ring sections are configured to be substantially coaxially aligned along an ejection axis; and detecting ions ejected though an aperture on an end cap of the ion trap.
Another such method may comprise receiving ions of a sample into an ion trap through an opening of a ring electrode, the opening extending along a radial direction of the ring electrode, wherein the radial direction is substantially perpendicular to an ejection axis of the ion trap; and detecting ions ejected though an aperture on an end cap of the ion trap.
The preceding summary is not intended to restrict in any way the scope of the claimed invention. In addition, it is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the invention, as claimed.
The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate various embodiments and exemplary aspects of the present invention and, together with the description, explain principles of the invention. In the drawings:
Reference will now be made in detail to exemplary embodiments of the invention, examples of which are illustrated in the accompanying drawings. When appropriate, the same reference numbers are used throughout the drawings to refer to the same or like parts.
Embodiments of the present disclosure may involve apparatuses, systems, and methods for performing mass analysis. As used herein, mass analysis refers to techniques of analyzing masses of molecules or particles of a sample material. Mass analysis may include mass spectrometry, in which a spectrum of the masses and their relative abundance of the molecules or particles are generated and/or displayed. Mass analysis can be used to determine the chemical composition of a sample, the masses of molecules/particles, and/or to elucidate the chemical structures of molecules. Mass analysis can be conducted by using a mass spectrometer. A mass spectrometer may generally comprise three main parts: (1) an ionizer to convert some portion of the sample into ions based on electron ionization, photoionization, thermal ionization, chemical ionization, desorption ionization, electro or nano spray ionization, and/or other suitable processes; (2) an ion trap that sorts the sample ions by mass (or more particularly, by mass-to-charge (m/z) ratio); and (3) a detector that measures the quantity of ions sorted and expelled by the ion trap.
Ion trap mass spectrometers take several forms. For example, ion traps may include 3D quadrupole ion traps, linear ion traps, and cylindrical ion traps, among others.
A 3D quadrupole ion trap (QIT) typically comprises a central, donut-shaped hyberboloid ring electrode and two hyperbolic end cap electrodes. In the most basic usage, the end caps are held at a static potential, and the RF oscillating drive voltage is applied to the ring electrode. Ion trapping occurs due to the formation of a three dimensional quadrupolar trapping potential well in the central intra-electrode region when appropriate time-dependent voltages are applied to the electrodes. The ions oscillating in the trap become unstable in the Z-direction of the well and are ejected from the trap in order of ascending m/z ratio as the RF voltage or frequency applied to the ring is ramped. The ejected ions can be detected by an external detector, for example an electron multiplier, after passing through an aperture in one of the end cap electrodes.
A linear ion trap (LIT) also traps ions in a quadrupolar field, but whereas a 3D trap is radially symmetric about the Z axis, a LIT incorporates a two dimensional quadrupolar field that extends lengthwise. An advantage of an LIT is its larger trapping volume. LIT electrodes may also be substantially hyperbolic or substantially rectangular, where the latter is referred to as a rectilinear ion trap.
A cylindrical ion trap (CIT) refers to an ion trap comprising planar end cap electrodes and a cylindrical ring electrode instead of hyperbolic electrode surfaces. A CIT can produce a field that is approximately quadrupolar near the center of the trap, thereby providing performance comparable to quadrupole ion traps having a donut-shaped hyberboloid ring electrode. CITs may be favored for building miniature ion traps and/or mass analysis devices because CITs are mechanically simple and can be more easily manufactured.
The techniques disclosed in this application can be applied, for example, to CITs, where the electrode(s) between the two end caps are substantially cylindrical. As used herein, such ring-shaped electrodes can also be referred to as center electrodes, as they are between the two end caps. However, the word center does not necessarily mean that these electrodes are in the exact center of the ion trap.
In some embodiments, ion trap component 10 may be formed by cutting out radial opening 28 from a single ring-shaped structure using techniques such as electric discharge machining, leaving the uncut portions between upper and lower ring sections 22 and 24 as connecting portions 32. In these embodiments, connecting portions 32 and ring sections 22 and 24 may be parts of a single body. Ions may be trapped inside ion trap component 10, for example, in the space defined by connecting portions 32 and ring sections 22 and 24. In some embodiments, ion trap component 10 may include only one connecting portion 32. For example, opening 28 may extend all the way towards the left or right side of ion trap component 10. In some embodiments, connecting portions 32 may be significantly distant from the inner boundary of axial opening 26 of ring electrode 20 so as not to distort the internal electric field generated by the ring electrode.
In
End caps 104 and 114 may comprise doped silicon, stainless steel, aluminum, copper, nickel plated silicon or other nickel plated materials, gold, and/or other electrically conductive materials, and may be formed by laser etching, LIGA, dry reactive ion etching (DRIE) and other types of etching, micromachining, and/or other manufacturing processes.
Apparatus 100 may include one or more ring electrodes. For example, in the embodiment depicted in
In some embodiments, ring sections 122 and 124 may be formed from a single ring structure. For example, ring sections 122 and 124 may be formed by at least partially splitting the single ring structure. In another example, ring sections 122 and 124 may be formed by creating a gap extending at least partially around the side of a single ring structure. The two ring sections 122 and 124 are not necessarily separate from each other. For example, they may connect to each other at least partially at one or more locations, such as at electrical connection 126 (e.g., connecting portion 32 in
Ring sections 122 and 124 may be electrically connected to each other by, for example, electrical connection 126. Electrical connection 126 may include a conductor physically connecting the two ring sections, or by means of continuous physical extension from one ring to the other (e.g., when the two rings are manufactured by splitting or creating a gap on a single ring structure, a partial splitting or a partial gap means that the two rings are still unseparated at some part). Electrical connection 126 makes ring sections 122 and 124 substantially equal electric potential.
Ring sections 122 and 124 may be substantially coaxial aligned along an ejection axis. For example, the coaxes of ring sections 122 and 124 may coincide with the axis of aperture 114, through which ions can be ejected from apparatus 100. The ejection axis may be defined as an axis along which ions exit the ion trap, sometimes referred to as Z axis. For example, in
Ring sections 122 and 124 may be separated by an opening 128, through which ions or light can enter into the ion trap. Opening 128 may include the physical void by virtue of the split ring sections 122 and 124. In some embodiments, opening 128 may include a pass way formed by materials disposed between ring sections 122 and 124. For example, opening 128 may be surrounded by isolating materials deposited on the opposite surfaces of ring sections 122 and 128. Opening 128 may also include a particle guide extending through the rings. Ions 142 may enter into apparatus 100 via opening 128.
Ring section 122 may have a different internal diameter than ring section 124. Ring section 122 may have a different thickness than ring section 124, thus causing opening 128 not to be equally spaced from end caps 102 and 112. These differences between ring sections 122 and 124 may introduce a hexapole field component to the ion trap. In other embodiments, the thicknesses and inner diameters of ring sections 122 and 124 may be the same.
Ring sections 122, 124, and end caps 102, 112 when employed, collectively define an internal volume of the apparatus 100. The internal volume may include one or more potential wells that can trap ions 142.
In some embodiments, apparatus 100 may include an injector or a source 162 to inject or provide ions in the ion trap through opening 128. For simplicity, device 162 is referred to herein as an injector but may also function as a source. Injector 162 may include a flow injector (e.g., ions are injected by means of physical flow of particles), electrical injector (e.g., ions are injected by means of electrical force), magnetic injector (e.g., ions are injected by means of magnetic force), or the combination thereof. In some embodiments, injector 162 may be included as part of apparatus 100. In other embodiments, injector 162 may be an external component with respect to apparatus 100 but can work together with apparatus 100.
In some embodiments, injector 162 may be configured to inject ions along a direction substantially perpendicular to the ejection axis 182. For example, ions may be injected into the ion trap along a trajectory 152. It is noted that trajectory 152 may include directions that are titled into or out of the page (e.g., trajectory 152 and ejection axis 182 may not be in the same plane but still substantially perpendicular to each other). In some embodiments, injector 162 may be configured to inject ions along a direction substantially non-perpendicular to the ejection axis 182. For example, ions may be injected into the ion trap along a trajectory 154. It is noted that trajectory 154 is not limited to left or right direction, but generally refers to any direction that is not perpendicular to the ejection axis 182 (e.g., trajectory 154 and ejection axis 182 may not be in the same plane). In some embodiments, injector 162 may be configured to inject ions along a trajectory or direction displaced from the ejection axis 182. For example, as shown in
In some embodiments, injector 162 may function as an ionization source. In such embodiments, injector 162 can be referred to as ionizer 162. Instead of injecting ions into apparatus 100, ionizer 162 may provide energy into the ion trap through opening 128 to ionize samples to ions within the ion trap. For example, ionizer 162 may include a UV lamp for photoionization, an electron ionization source, or other suitable ionization sources. By providing ionization energy through opening 128 on the side of the ring electrode, ion capture efficiency may be improved compared to providing energy through apertures on the end caps, at least because (1) opening 128 may be bigger than any apertures and (2) ions formed in a disk like region can be more easily captured than ions formed from an axially positioned ionization source. Similar to injecting ions into the ion trap, ionization energy may be applied substantially perpendicular to the ejection axis, substantially non-perpendicular to the ejection axis, or along a trajectory or direction displaced from the ejection axis (e.g., as shown in
In some embodiments, apparatus 100 may comprise an electron generator 192. Electron generator 192 may act as an ionizer (e.g., instead of or in addition to injector/ionizer 162) to generate electrons that enter into the ion trap through, for example, aperture 104. The electrons may be used to ionize neutral molecules inside the ion trap.
In some embodiments, apparatus 100 may comprise a biasing device 132 to electrically bias end cap 102, 112, or both. Bias device 132 may include active devices such as a voltage source, a signal generator, etc, to provide DC and/or AC bias signals. In some embodiments, bias device 132 may include passive devices such as a capacitor, a resistor, etc., to provide bias signals to end cap 102 and/or 112 through coupling with the signals applied to ring sections 122, 124. The bias signal generated by bias device 132 creates electrical field across the internal volume of apparatus 100, which may apply electrical force to ions 142 so that their trajectory may be changed in response to the bias signal.
For example, the bias signal may effectively change the trajectory of ions from 152 to 154. Without the bias signal, a positively charged ion can be injected into apparatus 100 along the direction indicated by 152. The ion may substantially keep that direction until the trapping electrical field starts to capture the ion. With the bias signal (e.g., assuming the direction of electrical field is from left to right, i.e., end cap 102 has a high potential than end cap 112), however, the ion will depart from trajectory 152 right after entering into apparatus 100 and start to fly towards the right (for a positively charged ion) or left (for a negatively charged ion), due to the electrical force applied to the ion. As a result, even if the ion is initially injected into the ion trap along a direction substantially perpendicular to the Z axis, the actual trajectory will become a non-perpendicular one due to the bias signal.
Return to
Detector 332 may include a single-point ion collector, such as a Faraday cup or electronic multiplier. In some embodiments, detector 332 may alternatively or additionally include a multipoint collector, such as an array or microchannel plate collector. Other suitable detectors may also be used.
In the foregoing description of exemplary embodiments, various features are grouped together in a single embodiment for purposes of streamlining the disclosure. This method of disclosure is not to be interpreted as reflecting an intention that the claims require more features than are expressly recited in each claim. Rather, as the following claims reflect, inventive aspects lie in less than all features of a single foregoing disclosed embodiment. Thus, the following claims are hereby incorporated into this description of the exemplary embodiments, with each claim standing on its own as a separate embodiment of the invention.
Moreover, it will be apparent to those skilled in the art from consideration of the specification and practice of the present disclosure that various modifications and variations can be made to the disclosed systems and methods without departing from the scope of the disclosure, as claimed. Thus, it is intended that the specification and examples be considered as exemplary only, with a true scope of the present disclosure being indicated by the following claims and their equivalents.
This application claims the benefits of priority to U.S. Provisional Application No. 61/798,734, filed on Mar. 15, 2013, the entire content of which is incorporated herein by reference.
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