Emission current measurement for superior instrument-to-instrument repeatability
11145502 · 2021-10-12
Assignee
Inventors
- Lawrence G. Baldwin (Hutto, TX, US)
- Johnathan Wayne Smith (Round Rock, TX, US)
- Edward B. McCauley (Austin, TX, US)
Cpc classification
H01J49/022
ELECTRICITY
International classification
Abstract
An ion source assembly is described that includes an electron source configured to inject electrons into an ion volume to ionize an atom or molecule in the ion volume, wherein the electron source includes a filament. A lens electrode is positioned adjacent the electron source and includes an opening configured to pass electrons therethrough from the electron source into the ion volume. A supply voltage source is coupled to the filament and configured to supply a first voltage to the filament, wherein the first voltage is operable to ionize the molecules in the ion volume. Further, a bias voltage source is coupled to the supply voltage source and configured to supply a bias voltage to the lens electrode. Electrons striking the lens electrode are thereafter returned to the filament.
Claims
1. An ion source assembly, comprising: an electron source configured to inject electrons into an ion volume to ionize an atom or molecule in the ion volume, wherein the electron source includes a filament; a lens electrode positioned adjacent the electron source and including an opening, wherein the opening is configured to pass electrons therethrough from the electron source into the ion volume; a supply voltage source coupled to the filament, wherein the supply voltage source is configured to supply a first voltage to the filament, wherein the first voltage is operable to ionize the molecules in the ion volume; and a bias voltage source coupled to the supply voltage source and configured to supply a bias voltage to the lens electrode, wherein electrons striking the lens electrode are returned to the filament.
2. The ion source assembly of claim 1, wherein the supply voltage source is configured to supply a second voltage to the filament, wherein the second voltage is inoperable to ionize the molecules in the ion volume.
3. The ion source assembly of claim 2, wherein the supply voltage source is configured to alternate between supplying the first voltage and the second voltage.
4. The ion source assembly of claim 2, wherein the first voltage is −70 volts and the second voltage is −20 volts.
5. The ion source assembly of claim 2, wherein the lens electrode voltage is equal to 15 volts when the supply voltage source supplies the first voltage, wherein the lens electrode voltage is equal to 65 volts when the supply voltage source supplies the second voltage.
6. The ion source assembly of claim 1, wherein the filament is electrically floated.
7. The ion source assembly of claim 1, wherein the lens electrode is electrically floated.
8. The ion source assembly of claim 1, wherein the ion volume is electrically grounded.
9. The ion source assembly of claim 1, wherein the bias voltage source includes a direct-current (DC) bias power supply.
10. The ion source assembly of claim 1, wherein the fixed voltage potential of the bias voltage source relative to the supply voltage source is 85 volts.
11. The ion source assembly of claim 1, wherein the electron source is configured to inject electrons into the ion volume at a fixed or variable duty cycle.
12. An ion source assembly, comprising: an electron source configured to emit electrons, wherein the electron source includes an electrically floated filament, wherein a first portion of the electrons enters an ion volume to ionize an atom or molecule in the ion volume; a lens electrode positioned adjacent the electron source, wherein the lens electrode is electrically floated; a supply voltage source coupled to the filament, wherein the supply voltage source is configured to supply a first voltage to the filament, wherein the first voltage is operable to ionize the molecules in the ion volume; and a bias voltage source coupled to the supply voltage source and configured to supply a bias voltage to the lens electrode; wherein the lens electrode is configured to collect a second portion of the electrons, wherein the second portion of the electrons flows back to the filament.
13. The ion source assembly of claim 12, wherein the supply voltage source is configured to supply a second voltage to the filament, wherein the second voltage is inoperable to ionize the molecules in the ion volume.
14. The ion source assembly of claim 13, wherein the first voltage is −70 volts and the second voltage is −20 volts.
15. The ion source assembly of claim 12, wherein the bias voltage remains at a fixed voltage potential relative to the supply voltage source.
16. The ion source assembly of claim 15, wherein the fixed voltage potential of the bias voltage source relative to the supply voltage source is 85 volts.
17. An ion source assembly, comprising: a filament configured to emit electrons via thermionic emission; a lens electrode surrounding the filament; a first power supply coupled to the filament, wherein the first power supply is configured to supply a first voltage output at a first voltage slew rate to the filament, wherein the first voltage output is operable to ionize molecules; a second power supply coupled to the lens electrode, wherein the second power supply is configured to supply a second voltage output at a second voltage slew rate to the lens electrode; and a first capacitor coupling the first voltage output to the second voltage output.
18. The ion source assembly of claim 17, further comprising a resistor coupled between the second voltage output and the lens electrode, wherein the first capacitor and the resistor are operable to align the first voltage slew rate with the second voltage slew rate.
19. The ion source assembly of claim 17, further comprising a second capacitor configured to couple the second voltage output to an electrical ground, wherein the second capacitor is operable to reduce relative instrument-to-instrument variability in electron lens capacitance.
20. The ion source assembly of claim 17, wherein the first power supply is configured to alternate between a high first voltage output and a low first voltage output, wherein the second power supply is configured to alternate between a high second voltage output and a low second voltage output, wherein the second voltage output remains at a fixed voltage potential relative to the first voltage output.
Description
BRIEF DESCRIPTION OF THE DRAWINGS
(1) For a more complete understanding of the present invention, reference is now made to the following descriptions taken in conjunction with the accompanying drawings, in which:
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DETAILED DESCRIPTION OF THE INVENTION
(13) Embodiments of systems and methods for improved emission current measurements are described herein and in the accompanying exhibits.
(14) The section headings used herein are for organizational purposes only and are not to be construed as limiting the described subject matter in any way.
(15) In this detailed description of the various embodiments, for purposes of explanation, numerous specific details are set forth to provide a thorough understanding of the embodiments disclosed. One skilled in the art will appreciate, however, that these various embodiments may be practiced with or without these specific details. In other instances, structures and devices are shown in block diagram form. Furthermore, one skilled in the art can readily appreciate that the specific sequences in which methods are presented and performed are illustrative and it is contemplated that the sequences can be varied and still remain within the spirit and scope of the various embodiments disclosed herein.
(16) All literature and similar materials cited in this application, including but not limited to, patents, patent applications, articles, books, treatises, and internet web pages are expressly incorporated by reference in their entirety for any purpose. Unless described otherwise, all technical and scientific terms used herein have a meaning as is commonly understood by one of ordinary skill in the art to which the various embodiments described herein belongs.
(17) It will be appreciated that there is an implied “about” prior to the temperatures, concentrations, times, pressures, flow rates, cross-sectional areas, etc. discussed in the present teachings, such that slight and insubstantial deviations are within the scope of the present teachings. In this application, the use of the singular includes the plural unless specifically stated otherwise. Also, the use of “comprise”, “comprises”, “comprising”, “contain”, “contains”, “containing”, “include”, “includes”, and “including” are not intended to be limiting. 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 present teachings.
(18) As used herein, “a” or “an” also may refer to “at least one” or “one or more.” Also, the use of “or” is inclusive, such that the phrase “A or B” is true when “A” is true, “B” is true, or both “A” and “B” are true. Further, unless otherwise required by context, singular terms shall include pluralities and plural terms shall include the singular.
(19) A “system” sets forth a set of components, real or abstract, comprising a whole where each component interacts with or is related to at least one other component within the whole.
(20) It is to be noted within this specification that the term “floating” refers to a circuit, power supply, or other electrical feature which does not possess a ground which is common with earth ground. Conductors, such as filaments and electron lenses, are also described as having a floating potential if they are connected electrically to another floating conductor. For example, a filament power supply used to heat a filament to incandescence may supply a few amperes of current at only one or two volts across the filament. If the power supply does not have its ground in common with earth ground, the entire circuit can be said to “float” as its potential is not established. Establishing a potential (relative to earth ground) can be accomplished by providing a bias voltage source which has its ground in common with earth ground. Likewise, an electron lens is not floating if its power supply has its ground connected to earth ground but is floating if its ground is connected to another floated circuit such as a floated filament power supply.
(21) U.S. Pat. No. 5,756,996, entitled “Ion Source Assembly for An Ion Trap Mass Spectrometer and Method,” issued May 26, 1998 (the “'996 Patent”), the disclosure of which is incorporated herein by reference, generally describes a gating mechanism for ion traps wherein the ionizing electron beam energy is changed from a first value wherein ions are generated, and a second value wherein ions are not generated.
(22) AGC (Automatic Gain Control) control methods for beam instruments are described in the '682 Patent, U.S. Pat. No. 7,507,954, entitled “Pulsed Ion Source for Quadrupole Mass Spectrometer Method,” issued Mar. 24, 2009, and U.S. Pat. No. 7,759,655, entitled “Pulsed Ion Source for Quadrupole Mass Spectrometer and Method,” issued Jul. 20, 2010, the disclosures of which are herein incorporated by reference. Unlike ion traps which use AGC to control ion formation at a batch level for a wide mass range, AGC for quadrupoles can control ion formation on a mass-to-mass basis while individual ions are being scanned by the multipole. This can be used to suppress non-target matrix ions for full scan experiments or prevent detector saturation for MRM experiments amongst other modes.
(23) The '996 Patent describes an electron gating scheme wherein a filament bias potential is switched between two different negative values. An electron lens potential is also switched between two different positive values. The switching is synchronized to happen at the same time, such that a constant potential difference is maintained between the filament and the electron lens. This allows the ability to turn the ionization process on and off without disruption of the emission regulation process. It requires four independent potentials and switching means for both channels. As such, the method and hardware employed in the '996 Patent synchronizes the gate times of the filament and electron lens. This results in the ability to gate the ionization process without unduly affecting the control (i.e., the precision) of emission current. This is largely due to the fact that the injection times are relatively long (e.g., within the millisecond time domain). The '996 Patent further describes systems which eliminate neutral noise formation during scan out of ions from an ion trap.
(24) Referring to the ion trap mass spectrometer 100 of
(25) In accordance with the present invention, the energy of the electrons leaving the filament 131 and entering the ion volume 124 is controlled so that it is sufficient to ionize sample molecules and helium 126 within the source volume 124 only during the ionization time. The electron source includes a filament 131 which is heated to emit electrons. The filament may comprise a refractory material such as tungsten, rhenium or another suitable alloy for thermionic emission. The heating current supplied to the filament 131 is from a floated power supply and is controlled to provide substantially constant electron emission. A filament shroud 132 is electrically common with filament 131 and assures that emission of electrons is at the opening 133. The energy of electrons entering the ion source volume 124 is controlled by the voltage between the filament 131 and the ion source volume 124. Seventy eV has been found to be an electron energy satisfactory for ionizing atoms and molecules, though higher or lower electron energies may be used. In accordance with the present invention, the filament voltage and/or excitation voltage is reduced to a voltage below the ionizing voltage for helium during nonionizing periods.
(26) Upon being emitted, a certain number of electrons will strike the filament shroud 132. These electrons will not be counted as emission current since they return to the floated filament supply and are of no consequence. On the contrary, electrons striking the electron lens 134 represent a path to earth ground and will be counted as emission current. These counted electrons do not take part in actual ionization within ion volume 124 and so may be referred to as representing false emission current. The number of electrons which will strike the electron lens 134 is variable and depends on the precise alignment of the filament 131, the magnets (not shown) driving the movement of the electrons into the ion volume 124, and/or any small changes in positions of other elements of the electron source 130. In this arrangement, as the loop is closed on emission current, emitted electrons which strike the electron lens 134 are counted as false emission current, affecting the ability to accurately and efficiently control the electron emission. Therefore, errors or switching noise can be introduced in the election emission control system which vary instrument to instrument, or if the device is disassembled and reassembled, resulting in varying emission measurement responses.
(27) In some embodiments, filament supply, filament shroud 132, and filament 131 derive their potential through an emission current sense resistor 136. A typical emission current value may be 50 microamperes using a current sense resistor of 1,000 ohms. In this arrangement, the electron source 130 comprises an electron lens 134 which does not derive its potential through the emission current sense resistor 136. Instead, the potential of electron lens 134 is controlled by an independent gate lens supply (not shown) which is referenced to earth ground. As such, electrons which strike the electron lens 134 subsequently have a path to earth ground and do not return to the filament supply.
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(29) Additionally, the energy of the electrons leaving the electron source 230 and entering the ion volume 224 is controlled so that it is sufficient to ionize sample molecules and helium 226 within the source volume 224 only during the ionization time. The electron source includes a filament 231 which is heated to emit electrons and is controlled to provide substantially constant electron emission. Filament shroud 232 assures that emission of electrons is at the opening 233. The energy of electrons entering the ion source volume 224 is controlled by the voltage between the filament 231 and the ion source volume 224. Although the ion volume is shown grounded, the ion volume may also be held at a slight e.g. 10 volts positive or negative potential relative to earth ground in order to control the energy of ions leaving the source. These techniques are well known in the art.
(30) Spectrometer 200 also incorporates an emission current sensing resistor 236 for measuring the current emitted from the filament 231 using the technique described above with reference to
(31) The non-switched DC bias voltage supply 240, such as an 85 V DC bias, can be applied between the filament 231 and the electron lens 234. The DC bias voltage supply 240 eliminates the need for separate a switched electron lens supply as is deployed by the prior art. By including the DC bias voltage supply 240, the electron lens 234 can be floated along with the filament 231. As such, the voltage switching of the filament 231 potential propagates to the electron lens 234 through the bias supply 240 without the need of separate synchronized power supplies. For example, when the filament potential is at −20 V, the electron lens is at +65 V. Conversely, when the filament is at −70V, the electron lens is at +15V, the difference being set by the bias voltage 240. This further eliminates the need for two power supplies having highly matched voltage characteristics on each rail, and ensures better matched slew rates (i.e., how accurately the potentials follow each other on the electrodes) between the filament 231 and electron lens 234 potentials, resulting in decreased noise signal in the emission sense circuitry. Furthermore, it results in more accurate sensing of the true emission current delivered to the ion volume. This emission control scheme can be deployed in a continuous or pulsed mode of operation. It is preferable that the diameter of the entrance aperture of ion volume 224 be equal in size or larger than the aperture of electron lens 234. This ensures a minimum of false electron emission sensing due to electron collisions with the ion volume 224 which also have an electrical path to earth ground.
(32) Referring to
(33) The sample molecules from the gas chromatograph 301 can be carried through a passage or orifice 310 into an ion volume 351 of the ion source 302 by a carrier gas, such as helium. It should be noted that the ion volume 351 could be any region where atoms or molecules are ionized. For example, the ion volume 351 could be a typical external ion source or it could be an ion trap or a quadrupole, octupole, or another multipole.
(34) An electron source such as a filament 362 powered by a filament supply 361 is biased by a voltage source 360. The filament 362 emits electrons which pass through a gate 357 as they are accelerated toward the grounded ion volume 351. It should be noted that any electron source could be used such as an electron field emitter or cold cathode, or electron generator array. The filament 362 can also be coupled to a reflector 358 so that the reflector 358 and the filament 362 are at the same potential in order to provide a uniform electric field between the filament and gate.
(35) Emitted electrons gain kinetic energy as they travel toward the ion volume 351 and subsequently ionize a portion of sample molecules existing within the confines of the ion volume 351. Voltage source 360 applies a voltage switchable between first and second voltages to the filament 362 and reflector while a DC bias supply 320 applies a bias voltage to the gate 357 in order to keep the voltage potential between the filament 362 and gate 357 constant. By keeping the voltage potential between the filament 362 and gate 357 constant, emitted electrons can be moved between energies which alternately permit ionization and limit ionization without affecting the potential differential and generating noise signals due to unmatched slew rates or offset potentials of the power supplies.
(36) Ions generated in the ion volume 351 are extracted and focused in a continuous manner by a set of lens elements 354, 355, and 356 and are drawn into the rods 350 of the quadrupole mass filter 304. A voltage source 330 applies radio frequency (RF) and DC potentials to the rods of the mass filter to allow for selective mass transmission to the detector 306, which can include an electron multiplier 352, an amplifier, and a means of converting this analog signal to a digital signal.
(37) Further, filament 362, reflector 358, and lens 357 may each be electrically floated such that the current emitted from the filament 362 can be accurately measured by a sensor 359, and the sensed current can be fed back to the filament supply 361. More specifically, in this embodiment, as the loop is closed on emission current, emitted electrons which strike the floated reflector 358 or floated gate 357, are returned to the filament supply 361 and are not counted as false emission current. Therefore, errors can be minimized in the election emission control system, resulting in more consistent emission measurement responses and improved instrument to instrument repeatability.
(38) While the embodiments shown by
(39) Shown in
(40) Shown in
(41) One difficulty which arises with non-trapping beam instruments, such as quadrupoles, is the need to pulse at higher frequencies such as 10 to 50 kHz in order to control ion populations using pulse width modulation. This can generate difficulties in controlling emission, since it is more difficult to match slew rates inherent in separate power supplies and associated load capacitances. However, as the switch times are much faster (10 kHz or above) the rise and fall time difference of the potentials for the electron lens and filament become significant at low duty cycles. In particular, the entire circuit for the floating filament must exhibit high isolation and minimal capacitance to ground. Even if great care is made in the isolation circuitry of the filament power supply, the switch time of the electron lens is generally much faster. By using a floating electron lens bias supply which rides on top of the filament potential as shown in
(42) As an alternative to the foregoing method of matching slew rates by virtue of floating the electron lens supply with the filament supply, it has been realized that slew rate matching in pulsed operation can be accomplished in a relatively simple way for multiple ground referenced power supplies.
(43) The above methods of slew rate matching allow a precise potential difference between the filament and electron lens during switching intervals. As described, this reduces noise in the feedback circuitry by largely eliminating positive and negative going spikes in potential difference of these two elements, and the resultant noise in the emission sense circuitry.
(44) Although the present invention and its advantages have been described in detail, it should be understood that various changes, substitutions and alterations can be made herein without departing from the spirit and scope of the invention as defined by the appended claims. Moreover, the scope of the present application is not intended to be limited to the particular embodiments of the process, machine, manufacture, composition of matter, means, methods and steps described in the specification. As one of ordinary skill in the art will readily appreciate from the disclosure of the present invention, processes, machines, manufacture, compositions of matter, means, methods, or steps, presently existing or later to be developed that perform substantially the same function or achieve substantially the same result as the corresponding embodiments described herein may be utilized according to the present invention. Accordingly, the appended claims are intended to include within their scope such processes, machines, manufacture, compositions of matter, means, methods, or steps.