The present disclosure in general relates to mass spectrometry and in particular to systems and methods for modulating the intensity of an ion beam employed in a mass spectrometer.
The present teachings are generally related to systems and methods for modulating an ion beam intensity in a mass spectrometer.
Mass spectrometry (MS) is an analytical technique for determining the structure of test chemical substances with both qualitative and quantitative applications. MS can be useful for identifying unknown compounds, determining the composition of atomic elements in a molecule, determining the structure of a compound by observing its fragmentation, and quantifying the amount of a particular chemical compound in a mixed sample. Mass spectrometers detect chemical entities as ions such that a conversion of the analytes to charged ions must occur during the sampling process.
In many mass spectrometers, there is a need for modulating the intensity of an ion beam, generated via ionization of a sample, as the ion beam propagates through the mass spectrometer.
In one aspect, a mass spectrometer is disclosed, which includes an ion path along which an ion beam can propagate, and an ion beam deflector positioned in the ion path and configured to modulate transfer of an ion beam received from an upstream section of the ion path to a downstream section thereof, said ion beam deflector comprising at least two electrically conductive electrodes positioned relative to one another to provide an opening through which the ion beam can pass, where the two electrodes are electrically insulated relative to one another so as to allow maintaining each electrode at a DC potential independent of a DC potential at which the other electrode is maintained.
In some embodiments, the ion deflector can be implemented as a plurality of conductive electrodes that are positioned relative to one another to allow deflecting an ion beam with a given charge polarity along one of at least two possible directions. A controller can be operably coupled to at least one voltage source that supplies voltages to the conductive electrodes of the ion deflector so as to adjust the pattern of voltages applied to those electrodes, e.g., the polarity of the voltages applied to those electrodes, so as to adjust the direction along which the ion beam is deflected. By way of example, as discussed in more detail below, in some embodiments, the ion deflector can include four conductive electrodes that are shaped and positioned relative to one another to provide two intersecting slits through which ions can pass. By adjusting the voltages (e.g., the polarity of the voltages) applied to the conductive electrodes, an ion beam of a given charge polarity can be deflected along two directions one which is within one of the slits and the other is within the other slit.
At least one DC voltage source is operably coupled to the two conductive electrodes for application of DC voltages thereto. The mass spectrometer further includes a controller in communication with said at least one DC voltage source for modulating DC voltages applied to said two electrically conductive electrodes so as to transition the DC potential difference across the two electrodes between a first level at which the ion beam passes substantially undeflected through said ion deflector and a second level at which the ion beam is deflected from said ion path.
By way of example, the two electrically conductive electrodes can be two conductive plates that are separated by a gap through which the ion beam can pass. The application of a DC voltage differential across the plates can generate an electric field that can cause the deflection of the ion beam passing through the gap. In other embodiments, the electrically conductive electrodes can be in the form of two rods that are separated from one another to allow the passage of an ion beam therebetween. A voltage differential applied across the two rods can be modulated so as to steer an ion beam passing between the rods along a direction of interest. In yet other embodiments, the electrically conductive electrodes can be in the form of two conductive plates that are separated from one another to provide a passageway through which can an ion beam can pass. A voltage differential applied across the plates can be adjusted to affect the propagation path of the ion beam, e.g., by deflecting the ion beam toward one of the electrodes.
In some embodiments, at least one beam-collecting electrode can be disposed downstream of the ion beam deflector for collecting the deflected ion beam.
In some embodiments, the mass spectrometer can include at least one evacuated chamber in which at least a portion of the ion path is disposed. For example, the mass spectrometer can include two evacuated chambers that are in fluid communication and are differentially pumped to be maintained at different pressures. In such embodiments, the ion deflector can be positioned between the two chambers to allow modulating the intensity of the ion beam travelling between those two chambers.
The ion beam deflector can be positioned between the two evacuated chambers. In some such embodiments, an ion lens can be positioned upstream of the ion deflector. In such embodiments, the DC voltage source can be configured to apply a voltage difference between the upstream ion lens and the ion deflector so as to generate an electric field therebetween for deflecting the ion beam as it passes through the ion deflector.
The mass spectrometer can further include a controller that is configured to control the voltage source to adjust the voltages applied to the conductive electrodes of the ion deflector so as to modulate the transmission of the ion beam through the ion deflector. By way of example, the controller can cause the voltage source to apply substantially similar voltages or different voltages to the two conductive electrodes of the ion deflector so as to allow the ion beam to pass substantially undeflected through the ion beam deflector or to cause the deflection of the ion beam as it passes through the ion deflector, respectively. In some embodiments, the conductive electrodes can be formed of a suitable metal, such as, stainless steel, copper, copper alloys, gold-plated ceramics, and gold-plated PCB, and molybdenum alloys.
By way of example, the controller can cause the voltage source to apply a voltage differential across the two electrodes of the ion deflector so as to deflect the ion beam by a deflection angle, e.g., a deflection angle in a range of about 5 to about 60 degrees, though other deflection angles can also be utilized. In some embodiments, the controller can control the voltage source such that it applies a voltage differential across the two electrodes so as to substantially inhibit the passage of the ion beam from one evacuated chamber to another evacuated chamber between which the ion deflector is positioned.
In some embodiments, the ion beam deflector can be in the form of an ion lens having an opening through which ions can pass. In some such embodiments, the ion lens can be formed as two electrically conductive electrodes (e.g., two semi-circular electrodes) that are insulated from one another and separated so as to provide at least one opening for passage of the ion beam therethrough. By way of example, the two conductive electrodes can be separated by a slit through which the ion beam can pass.
In some embodiments, the first chamber can be maintained at a pressure in a range of about 0.1 Torr to about 10 Torr and the second chamber can be maintained at a pressure in a range of about 0.001 Torr to about 0.1 Torr.
In some embodiments, a set of rods arranged in a multipole configuration providing a passageway through which ions can pass, may be disposed in any of the evacuated chambers. In some embodiments, DC and/or RF voltages can be applied to the multipole rods, e.g., via one or more DC and/or RF voltage sources, such that the rod set functions as an ion guide and/or a mass analyzer.
In some embodiments, a controller can control the DC voltages applied to the conductive electrodes of an ion deflector according to the present teachings so as to steer an ion beam in a direction of interest. For example, the controller can cause a switching of the polarities of the voltages applied to two conductive electrodes separated from one another to provide a slit through which ions pass in order to change the direction along which the ions are deflected. By way of example, in some embodiments, an ion deflector according to the present teachings can include four conductive electrodes, e.g., four wedge-shaped conductive electrodes, that are positioned relative to one another so as to provide intersecting slits. By adjusting voltages applied to the conductive electrodes, an ion beam can be steered along different directions, e.g., right, left, up or down.
In a related aspect, a mass spectrometer is disclosed, which comprises an ion path along which an ion beam can propagate, an ion beam deflector positioned in said ion path and configured to modulate transfer of an ion beam received from an upstream section of the ion path to a downstream section thereof, said ion beam deflector comprising at least one electrically conductive electrode, at least one DC voltage source operably coupled to said at least one electrically conductive electrode for application of DC voltages thereto, and a controller in communication with said at least one DC voltage source for modulating DC voltages applied to said at least one electrically conductive electrode so as to transition the DC voltage applied to said at least one electrode between a first level at which the ion beam passes substantially undeflected through said ion deflector and a second level at which the ion beam is deflected from said ion path. In some embodiments, the at least one electrically conductive electrode includes a single electrode positioned either above or below the ion path. In some embodiments, the DC voltage at the second level is configured to cause a deflection of the ion beam relative to the ion path at an angle in a range of about 5 to about 60 degrees.
In some embodiments, an ion lens is positioned upstream of the ion beam deflector and the controller is configured to cause said at least one DC voltage source to adjust a DC voltage applied to said at least one electrically conductive electrode between a first level at which the at least one electrically conductive electrode and the ion lens are maintained at the same electric potential to allow the ion beam to pass undeflected through the ion beam deflector and a second level at which the at least one electrically conductive electrode and the ion lens are maintained at different electric potentials to cause the ion beam to deflect as the ion beam passes through the ion beam deflector.
In one aspect, a method for modulating intensity of an ion beam propagating along an ion path is disclosed, which includes passing the ion beam relative to an electrically conductive electrode to which a DC voltage is applied and modulating the applied DC voltage, e.g., at a duty cycle in a range of about 0.001 to about 1, between a first level at which the ion beam continued propagating substantially undeflected along its propagation path and a second level at which the ion beam is deflected from its propagation path.
In a related aspect, a method for modulating intensity of an ion beam propagating along an ion path is disclosed, which includes passing the ion beam between two electrodes insulated from one another to allow sustaining a DC potential difference therebetween, and modulating the DC potential difference across the two electrodes between at least a first level and a second level such that when the DC potential difference is at said first level the ion beam continues propagating substantially undeflected along its path and when the DC potential difference is at said second level the ion beam is deflected from its propagation path.
In some embodiments of the above method, the DC voltage differential applied across the electrodes of the ion deflector can be modulated at a duty cycle, e.g., in a range of about 0.001 to about 1.
Further understanding of various aspects of the present teachings can be obtained by reference to the following detailed description in conjunction with the associated drawings, which are described briefly below.
It will be appreciated that for clarity, the following discussion will explicate various aspects of embodiments of the present disclosure, while omitting certain specific details wherever convenient or appropriate to do so. For example, discussion of like or analogous features in alternative embodiments may be somewhat abbreviated. Well-known ideas or concepts may also for brevity not be discussed an any great detail. One of ordinary skill will recognize that some embodiments of the present disclosure may not require certain of the specifically described details in every implementation, which are set forth herein only to provide a thorough understanding of the embodiments. Similarly it will be apparent that the described embodiments may be susceptible to alteration or variation according to common general knowledge without departing from the scope of the disclosure. The following detailed description of embodiments is not to be regarded as limiting the scope of the applicant's teachings in any manner.
As used herein, the terms “about” and “substantially equal” refer to variations in a numerical quantity that can occur, for example, through measuring or handling procedures in the real world; through inadvertent error in these procedures; through differences in the manufacture, source, or purity of compositions or reagents; and the like. Typically, the terms “about” and “substantially” as used herein means 10% greater or lesser than the value or range of values stated or the complete condition or state. For instance, a concentration value of about 30% or substantially equal to 30% can mean a concentration between 27% and 33%. The terms also refer to variations that would be recognized by one skilled in the art as being equivalent so long as such variations do not encompass known values practiced by the prior art.
As used herein the term “and/or” includes any and all combinations of one or more of the associated listed items and may be abbreviated as “/”.
With reference in
As shown in
In order to stop the passage of the ion beam from chamber 10 into chamber 12, a differential voltage can be applied across the two ion lenses 14 and 16, as shown in
By modulating the voltage differential applied between the two ion lenses, the passage of the ion beam between the two chambers 10 and 12 can be modulated. By way of illustration,
As discussed in more detail below, in embodiments, rather than causing reversal and impingement of an ion beam on a lens surface, a plurality of conductive electrodes (herein also referred to as ion deflection electrodes) can be employed such that the ion beam can be deflected, via application of appropriate voltages to those electrodes, as the ion beam passes through a gap provided between the two electrodes.
In some embodiments, the deflection angle of the ion beam is such that the ion beam is inhibited from entering the second chamber. By modulating a voltage differential applied between the deflection electrodes, the passage of the ion beam from the first chamber to the second chamber can be controlled. As discussed further below, the ion deflection electrodes may have different shapes and configurations. By way of example, in some embodiments, the ion deflection electrodes can be in the form of two plates that are separated from one another by a gap through which the ion beam can pass. In other embodiments, the conductive electrodes can be in the form of two portions of an ion lens that are insulated relative to one another and include an opening therebetween through which the ion beam can pass. Other suitable shapes and/or arrangements of the conductive electrodes can also be employed.
The ion deflector assembly 300 includes an ion lens 302 having an opening 302a through which ions can pass and an ion deflector 304 according to an embodiment of the present teachings, which is disposed downstream of the ion lens 302. In this embodiment, the ion deflector 304 includes two semi-circular conductive electrodes 304a/304b that are separated from one another to form a slit 304c therebetween through which ions can pass. Further, the semi-circular portions are electrically insulated from one another to allow the application of independent voltages to the conductive portions so as to modulate the electric field within the slit, thereby affecting the propagation path of the ions passing through the slit. For example, as shown in
In contrast,
In some embodiments, the ion deflection assembly can include an ion collection electrode for collecting the ions deflected via passage through the ion deflection assembly. For example,
One or more DC and/or RF voltage sources (not shown in the figure) can apply DC and/or RF voltages to the two rod sets such that they can provide their respective functions, e.g., as an ion guide and/or a mass analyzer. Although in this embodiment the chambers 400 and 402 house rod sets, in other embodiments other devices can be disposed in any of these chambers. In other words, the present teachings are not limited to modulating an ion beam that passes through multipole rod sets, but can be more generally applied for deflecting an ion beam along its propagation path.
The chamber 400 extends from an inlet 400a to an outlet 400b and chamber 402 extends from an inlet 402a to an outlet 402b. The outlet 400b of the chamber 400 is in fluid communication with the inlet 402a of the chamber 402 to allow the passage of ions from the chamber 400 into the chamber 402. In this embodiment, an ion deflector assembly 404 is positioned between the outlet 400b of the chamber 400 and the inlet 402a of the chamber 402. The ion deflector assembly 404 includes an ion lens 405 that can provide focusing of ions passing therethrough and an ion deflector 407 that can modulate the transfer of an ion beam from the chamber 400 into the chamber 402. An ion collection electrode 409 is positioned downstream of the ion deflector 407 to capture ions that are deflected by the ion deflector 407.
With particular reference to
Referring again to
A controller 412 in communication with the voltage sources 410a/410b can control those voltage sources so as to adjust voltage 1 and voltage 2. For example, the controller can cause the adjustment of voltages 1 and 2 so as to control the transmission of an ion beam IB from the chamber 401 into the chamber 402.
For example, as shown in
In contrast, as shown in
Further, rather than inhibiting the transfer of the ion beam between the two chambers, a voltage differential applied across the ion lens 405 and the combination of the ion deflector 407 and the ion collection electrode 409 can be adjusted so as to inhibit the passage of a portion of the ions into the chamber 402 while allowing other ions in the ion beam to reach the chamber 402 substantially undeflected, thereby modulating the intensity of the ion beam as it passes from chamber 400 into the chamber 402. By way of example, a deflection voltage differential across the ion lens 405 and the combination of the ion deflector 407 can be selected such that the deflection angle is small enough, e.g., an angle less than about 5 degrees, such as 1 degree, such that some of the ions are inhibited from passing into the chamber 402 while other ions in the beam continues to reach the downstream chamber 402.
By way of example,
In some embodiments, the length of the plates 1000a/1000b and the applied voltage can be selected so as to allow the deflected ions to leave the passageway and be optionally captured by an ion collection electrode, e.g., in a manner discussed above. In other embodiments, the length of the plates and the applied electric field can be selected such that the deflected ions (or at least a portion thereof) strike one of the plates and hence do not exit the ion deflector.
In some implementations, a periodic modulation of the DC voltage differential applied across the plates can result in a periodic modulation of the intensity of the ion beam passing between the ion guide 1 and the ion guide 2.
The DC voltages applied to the conductive electrodes of the ion deflector 2000 can be adjusted, e.g., under control of a controller such as those disclosed herein, so as to deflect the ion beam in a desired direction (e.g., up, down, right or left) as the ions pass through the slits 2000a/2000b.
For example, when the voltages 1, 2, 3 and 4 applied to the conductive electrodes 2001/2002/2003/2004 of the ion deflector are equal, the ion beam will pass through the ion deflector without any deflection. Typically, the ion guide 2 is aligned relative to the ion deflector such that the ion beam will pass through the center of the ion beam deflector (i.e., the intersection of the two slits), when the voltages applied to the conductive electrodes of the ion deflector are equal. By way of example, in order to steer a positive ion beam propagating through the ion guide 1 towards ion guide 2 beam to the right, the magnitudes of the voltages applied to the conductive electrodes of the ion deflector can be the same with the voltages V1 and V2 having a positive polarity and the voltages V3 and V4 having a negative polarity.
In contrast, for steering the ion beam to the left, the voltages V1, V2, V3 and V4 can have the same magnitude with the voltages V3 and V4 having a positive polarity and the voltages V1 and V2 having a negative polarity. For steering the ion beam in an upward direction, the magnitudes of the voltages V1, V2, V3, and V4 can be the same with the voltages V2 and V3 having a positive polarity and the voltages V1 and V4 having a negative polarity and for steering the ion beam in a downward direction, the magnitudes of the voltages V1, V2, V3, and V4 can be the same with the voltages V1 and V4 having a positive polarity and the voltages V2 and V3 having a negative polarity.
The above ion deflector 2000 allows changing the direction of ion deflection from time to time. More specifically, the above ion deflector allows deflecting an ion beam along each of the following four directions: left, right, up and down. In some embodiments, by changing the direction of ion deflection from time to time, potential contamination caused by the deflected ions and their adverse effects may be minimized, and preferably eliminated. By way of example, a controller operably to the ion deflector 2000 can be programmed to modify the pattern of voltages applied to the four conductive electrodes of the ion deflector, e.g., based on a predefined temporal schedule, to change the deflection of the ion beam between the above four directions.
By way of further illustration,
A voltage differential applied between the two rods 3001/3002 can be adjusted to modulate the propagation path of the ion beam. By way of example, when the voltages V1 and V2 applied to the rods 3001 and 3002, respectively, are equal (i.e., when the voltage differential between the two rods is zero), the ion beam passes through the ion deflector undeflected. For deflecting an ion beam with a positive polarity upward as the ion beam reaches the ion deflector via passage through the ion guide 1, the voltages V1 and V2 can have the same magnitudes with positive and negative polarities, respectively. In contrast, for deflecting the ion beam downward, the voltages V1 and V2 can have the same magnitudes with negative and positive polarities, respectively. It should be understood that other configurations of the voltages can also be utilized to achieve a desired deflection (steering) of the ion beam. For example, the applied voltages may have different magnitudes.
An ion deflector according to the present teachings can be incorporated in a variety of mass spectrometers. By way of example, with reference to
At least a portion of the ions pass through an orifice 31 of an orifice plate 30 into a chamber 121 in which an ion guide 140 (herein also referred to as QJet® ion guide) is disposed.
The chamber 121 can be maintained, for example, at a pressure in a range of about 1 torr to about 3 torr. The QJet® ion guide includes four rods (two of which 130 are visible in the figure) that are arranged according to a quadrupole configuration to provide a passageway therebetween through which the ions can pass. RF voltages can be applied to the rods of the QJet® ion guide, e.g., via capacitive coupling to a downstream ion guide Q0 discussed further below or via an independent RF voltage source, for radially confining, and focusing the ions for transmission to a downstream chamber 122 in which an ion filter 108 according to an embodiment of the present teachings is disposed.
In this embodiment, an ion deflector assembly 107 such as that discussed above in connection with
The chamber 122 can be maintained at a pressure lower than the pressure at which the chamber 121 is maintained. By way of example, the chamber 122 can be maintained at a pressure in a range of about 2 mTorr to about 15 mTorr. In this embodiment, an ion guide Q0 is positioned in the chamber 122. The ion guide Q0 includes a plurality of rods (not shown in the figure) that are arranged in a multipole configuration. An RF voltage source 197 applies RF voltages to the rods of the Q0 ion guide for providing radial confinement of the ions passing therethrough
In this embodiment, a DC voltage source 193a applies a DC voltage to the ion lens of the ion deflector assembly 107 (See, ion lens 405 discussed above) and a DC voltage source 193b applies a DC voltage to the combination of the ion deflector and the ion collection electrode of the ion deflector assembly (See, ion deflector 407 and ion collection electrode 409). In some embodiments, the DC voltage source can also be employed to apply DC voltages to the rods of the Q0 ion guide, e.g., to generate a voltage differential between the QJET and Q0 ion guides to accelerate the ions exiting the QJET ion guide towards the Q0 ion guide.
A controller 3000 controls the operation of the RF voltage source 197 as well as the DC voltage sources 193a and 193b. In particular, the controller can control the operation of the DC voltage sources 193a and 193b so as to modulate the transmission of ions between the evacuated chambers 121 and 122, e.g., in a manner discussed herein.
A mass analyzer Q1110 receives the ions passing through the ion guide Q0 via an ion lens IQ1 and one stubby lens ST1. In this embodiment, the mass analyzer Q1110 includes four rods that are arranged in a quadrupole configuration and to which RF and/or DC voltages can be applied for selecting ions having m/z ratios within a target range. The ions propagating through the mass analyzer Q1110 (herein referred to as precursor ions) pass through stubby lenses ST2 and ion lens IQ2 to reach a collision cell 112 (q2).
At least a portion of the precursor ions are fragmented in the collision cell 112 to generate a plurality of product ions. The product ions pass through an ion lens IQ3 and a stubby lens ST3 to reach another downstream mass analyzer Q3. In this embodiment, the mass analyzer Q3 includes four rods that are arranged in a quadrupole configuration and to which RF and/or DC voltages can be applied to allow passage of product ions having an m/z ratio of interest. The product ions passing through the mass analyzer Q3 pass through an exit lens 115 to be detected by an ion detector 118. In some embodiments, the quadrupole mass analyzer Q3 can be replaced with a time-of-flight (ToF) mass analyzer or any other suitable mass analyzer. An analysis module 119 can receive the detection signals generated by the ion detector 118 and process those signals to generate a mass spectrum of the detected ions.
A controller 3000 in communication with the voltage sources 193a and 193b can control these voltage sources to adjust the voltages applied to the ion lens and the combination of the ion deflector and the ion collection electrode to modulate the passage of an ion beam between the QJET and Q0 ion guides, in a manner discussed above. The controller 3000 can also control the operation of the RF voltage source. In addition, in embodiments in which the voltage source 193a and/or 193b are used to apply DC voltages to the rods of the ion guides and/or mass analyzers of the mass spectrometer, the controller 3000 can also control the voltage sources so as to adjust the voltages applied to those devices.
With reference to
The conductive electrode 901 can be biased via application of a DC bias voltage thereto to repel the ions in the beam as they pass through, thereby deflecting the ion beam away from the electrode, as shown schematically in
By way of example, the embodiment depicted in
With reference to
The controller 3000 can be implemented in hardware, firmware and/or software using known techniques in the art as informed by the present teachings.
By way of example,
The bus 500d allows communication between the processor and various other components of the controller. In this example, the controller 500 can further include a communications module 500e that is configured to allow sending and receiving signals.
Instructions for use by the controller 500, e.g., for adjusting the DC voltages applied to the auxiliary electrodes, can be stored in the permanent memory module 500b and can be transferred into the transient memory module 500c during runtime for execution. The controller 500 can also be configured to control the operation of other components of the mass spectrometer, such as the ion guide, and mass analyzer, among others.
The present teachings can provide advantages relative to conventional techniques for adjusting an intensity of the ion beam. For example, the modulation of an ion beam using the present teachings can provide a more homogeneous ion beam than conventional pulsing techniques employed for reducing the intensity of an ion beam, e.g., as it passes from one ion chamber into an downstream chamber while reducing, and preferably eliminating, contamination of ion optics positioned between the two chambers.
Those having ordinary skill will appreciate that various changes can be made to the above embodiments without departing from the scope of the present teachings.
The present application claims priority to provisional application number U.S. 63/249,944 filed on Sep. 29, 2021, which is herein incorporated by reference in its entirety.
Filing Document | Filing Date | Country | Kind |
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PCT/IB2022/059261 | 9/28/2022 | WO |
Number | Date | Country | |
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63249944 | Sep 2021 | US |