# US 9,520,280 B2 · Ion detection > Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt - Number: US 9,520,280 B2 - Document ID: US9520280B2 - Status: Granted - Kind: B2 - Application number: 13/993,316 - Filed: 2011-12-14 - Published: 2013-10-10 - Granted: 2016-12-13 - Earliest claimed: 2010-12-14 - Assignees: Thermo Fisher Scientific (Bremen) GmbH - Applicants: Alexander A. Makarov - Inventors: Alexander A. Makarov - Web page: https://patentgrep.com/patent/US9520280B2 ## CPC - H01J 49/282: {using electrostatic analysers} - H01J 49/027: {detecting image current induced by the movement of charged particles (H01J49/38 takes precedence)} - H01J 49/08: Electron sources, e.g. for generating photo-electrons, secondary electrons or Auger electrons - H01J 49/38: Omegatrons {; using ion cyclotron resonance} - H01J 49/4245: {Electrostatic ion traps (H01J49/422 takes precedence)} - H01J 49/425: {with a logarithmic radial electric potential, e.g. orbitraps} - H01J: ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS (spark-gaps H01T; electric arc lamps H05B31/00; particle accelerators H05H) ## Abstract Mass analyzers and methods of ion detection for a mass analyzer are provided. An electrostatic field generator provides an electrostatic field causing ion packets to oscillate along a direction. A pulse transient signal is detected over a time duration that is significantly shorter than a period of the ion oscillation or using pulse detection electrodes having a width that is significantly smaller than a span of ion harmonic motion. A harmonic transient signal is also detected. Ion intensity with respect to mass-to-charge ratio is then identified based on the pulse transient signal and the harmonic transient signal. ## Claims ### Claim 1 A mass analyzer, comprising: an electrostatic field generator, arranged to provide an electrostatic field causing ion packets to oscillate along a longitudinal direction with a period, the electrostatic field generator including an outer electrode coaxial with at least an inner electrode, at least one of the out electrode assembly and the inner electrode assembly including a plurality of electrode segments; a pulse detection electrode arrangement including at least one pulse detection electrode, the at least one pulse detection electrode being an electrode segment of the plurality of electrode segments located near a center of the electrostatic field generator in the longitudinal direction, the pulse detection electrode arrangement configured to detect a pulse transient signal over a time duration that is significantly shorter than the period of the ion packet oscillation; a harmonic detection electrode arrangement including two or more harmonic detection electrodes, the harmonic detection electrodes being electrode segments of the plurality of electrode segments located near the ends of the electrostatic field generator in the longitudinal direction, the harmonic detection electrode arrangement configured to detect a harmonic transient signal continuously over a time duration which is at least 30% relative to the total time of ion packet harmonic motion; and a processor, configured to identify ion intensity with respect to mass-to-charge ratio, based on the pulse transient signal and the harmonic transient signal wherein a width in the longitudinal direction of a pulse detection electrode of the pulse detection electrode arrangement is significantly smaller than a width in the longitudinal direction of a harmonic detection electrode arrangement. ### Claim 2 (depends on 1) The mass analyzer of claim 1, wherein the harmonic detection electrode arrangement is located at least at the turning points of ion packets in the longitudinal direction and wherein the a harmonic transient signal comprises an image current. ### Claim 3 (depends on 2) The mass analyzer of claim 2, wherein the harmonic detection electrode arrangement comprises a plurality of electrodes, each of the plurality of electrodes being maintained at different potentials. ### Claim 4 (depends on 1) The mass analyzer of claim 1, wherein the harmonic detection electrode arrangement is configured to detect a harmonic transient signal continuously over a time duration which is at least 50% relative to the total time of ion packet harmonic motion. ### Claim 5 (depends on 1) The mass analyzer of claim 1, wherein the pulse detection electrode arrangement comprises at least one pulse detection electrode, each of the at least one pulse detection electrodes having a width in the longitudinal direction that is significantly smaller than the span of harmonic motion. ### Claim 6 (depends on 1) The mass analyzer of claim 1, wherein the processor is configured to identify ion intensity with respect to mass-to-charge ratio by processing of the pulse transient signal using at least one of: auto-correlation; linear prediction; filter diagonalization method; any other harmonic inversion method; and wavelet transformation. ### Claim 7 (depends on 1) The mass analyzer of claim 1, wherein the processor is further configured to identify ion intensity with respect to mass-to-charge ratio by processing of the harmonic transient signal using at least one of: Fourier transformation; linear prediction method; filter diagonalization method; and any other harmonic inversion method. ### Claim 8 (depends on 1) The mass analyzer of claim 1, wherein the pulse detection electrode arrangement comprises at least one detection electrode having a width in the longitudinal direction such that ion packets transit near the at least one detection electrode for a duration that is substantially shorter than the half-period of the ion packet oscillation. ### Claim 9 (depends on 1) The mass analyzer of claim 1, wherein the electrostatic field generator is arranged to provide the electrostatic field between the outer electrode and the inner electrode. ### Claim 10 (depends on 9) The mass analyzer of claim 9, wherein the pulse detection electrode arrangement is formed using at least a part of at least one of: the inner electrode and the outer electrode; and wherein the pulse transient signal comprises an image current detected at the pulse detection electrode arrangement. ### Claim 11 (depends on 10) The mass analyzer of claim 10, wherein at least one of: the inner electrode; and the outer electrode comprises a first side electrode portion, a second side electrode portion and a central electrode portion located between the first and second side electrode portions and separated therefrom by electrically insulating portions, the pulse detection electrode arrangement being formed from the central electrode portion. ### Claim 12 (depends on 11) The mass analyzer of claim 11, wherein the at least one of: the inner electrode; and the outer electrode is formed from an insulator, the first and second side electrode portions and the central electrode portion being formed from metallization on the surface of the insulator. ### Claim 13 (depends on 11) The mass analyzer of claim 11, wherein the at least one of: the inner electrode; and the outer electrode is configured such that the resistance between each of the first and second side electrode portions and the central electrode portion is at least 100 MΩ. ### Claim 14 (depends on 12) The mass analyzer of claim 12, wherein the insulator is made from glass. ### Claim 15 (depends on 11) The mass analyzer of claim 11, further comprising: a conductor, arranged to provide the pulse transient signal to the edge of the at least one of: the inner electrode; and the outer electrode, the conductor being formed by metallization on the surface of the insulator. ### Claim 16 (depends on 11) The mass analyzer of claim 11, further comprising: a conductor, arranged to provide the pulse transient signal to the edge of the at least one of: the inner electrode; and the outer electrode, the conductor being formed outside the volume in which ions are trapped. ### Claim 17 (depends on 11) The mass analyzer of claim 11, wherein the central electrode portion comprises a first central electrode part and a second central electrode part, the pulse transient signal comprising a combination of an image current generated in the first central electrode part and an image current generated in the second central electrode part. ### Claim 18 (depends on 9) The mass analyser of claim 9, wherein the pulse detection electrode arrangement comprises: a conversion electrode mounted interior to the mass analyser, the electrostatic field being configured such that ion packets hit the conversion electrode, causing secondary electrons to be emitted; a grid electrode mounted exterior to the mass analyser and located to receive the secondary electrons from the conversion electrode; a dynode, arranged to receive secondary electrons from the grid electrode; and microchannel plates, arranged to detect secondary electrons received from the dynode. ### Claim 19 (depends on 18) The mass analyser of claim 18, wherein the conversion electrode is spatially separated from the inner electrode and the outer electrode. ### Claim 20 (depends on 1) The mass analyzer of claim 1, wherein the pulse detection electrode arrangement comprises a first pulse detection electrode and a second pulse detection electrode, the mass analyzer further comprising a pulse differential amplifier, arranged to provide the pulse transient signal based on the difference between a detection signal generated in the first pulse detection electrode and a detection signal generated in the second pulse detection electrode. ### Claim 21 (depends on 1) The mass analyzer of claim 1, wherein the harmonic detection electrode arrangement comprises a first harmonic detection electrode and a second harmonic detection electrode, the mass analyzer further comprising a harmonic differential amplifier, arranged to provide the harmonic transient signal based on the difference between an image current generated in the first harmonic detection electrode and an image current generated in the second harmonic detection electrode. ### Claim 22 A method of ion detection for a mass analyzer in which ions are caused to form ion packets that oscillate within an electrostatic field generator along a longitudinal direction with a period, the electrostatic field generator including an outer electrode coaxial with at least an inner electrode, at least one of the outer electrode assembly and the inner electrode assembly including a plurality of electrode segments, the method comprising: detecting a pulse transient signal over a time duration that is significantly shorter than the period of the ion packet oscillation using at least one pulse detection electrode, the pulse detection electrode being an electrode segment of the plurality of electrode segments near the center of the oscillation in the longitudinal direction; detecting a harmonic transient signal continuously over a time duration which is at least 30% relative to the total time of ion packet harmonic motion using two or more harmonic detection electrodes, the harmonic detection electrodes being electrode segments of the plurality of electrode segments and positioned near the ends of the oscillation in the longitudinal direction; and identifying ion intensity with respect to mass-to-charge ratio, based on the harmonic transient signal and the pulse transient signal, wherein a width in the longitudinal direction of the pulse detection electrode is significantly smaller than a width in the longitudinal direction of the harmonic transient detection electrode arrangement. ### Claim 23 (depends on 22) The method of claim 22, wherein the harmonic transient signal comprises an image current signal detected at least at the turning points of ion packets in the longitudinal direction. ### Claim 24 (depends on 23) The method of claim 23, wherein each of the harmonic detection electrodes is maintained at different potentials. ### Claim 25 (depends on 22) The method of claim 22, wherein the step of detecting a harmonic transient signal comprises detecting a harmonic transient signal continuously over a time duration which is at least 50% relative to the total time of ion packet harmonic motion. ### Claim 26 (depends on 22) The method of claim 22, wherein each of the at least one pulse detection electrodes has a width in the longitudinal direction that is significantly smaller than the span of harmonic motion. ### Claim 27 (depends on 22) The method of claim 22, wherein the step of identifying ion intensity with respect to mass-to-charge ratio comprises processing the pulse transient signal using at least one of: auto-correlation; linear prediction; filter diagonalization method; and wavelet transformation. ### Claim 28 (depends on 27) The method of claim 27, wherein the step of identifying ion intensity with respect to mass-to-charge ratio further comprises processing of the harmonic transient signal using at least one of: Fourier transformation; filter diagonalization method; and any other harmonic inversion method. ### Claim 29 A method of ion detection for a mass analyzer in which ions are caused to form ion packets that oscillate along a longitudinal direction with a period, the method comprising: detecting a pulse transient signal over a time duration that is significantly shorter than the period of ion packet oscillation using at least one pulse detection electrode near the center of the oscillation in the longitudinal direction; detecting a harmonic transient signal continuously over a time duration which is at least 30% relative to the total time of ion packet harmonic motion using two or more harmonic detection electrodes positioned near the ends of the oscillation a in the longitudinal direction; and identifying ion intensity with respect to mass-to-charge ratio including: processing the pulse transient signal to identify a preliminary set of frequencies and associated intensities using at least one of auto-correlation; linear prediction; filter diagonalization method; and wavelet transformation; and processing the harmonic transient signal together with the preliminary set of frequencies and associated intensities to determine ion intensity with respect to mass-to-charge ratio; wherein a width in the longitudinal direction of the pulse detection electrode is significantly smaller than a width in the longitudinal direction of the harmonic transient detection electrode arrangement. ### Claim 30 (depends on 29) The method of claim 29, wherein the step of processing the harmonic transient signal together with the preliminary set of frequencies and associated intensities uses a filter diagonalization method. ### Claim 31 (depends on 22) The method of claim 22, wherein the step of detecting a pulse transient signal uses a pulse detection electrode arrangement comprising at least one detection electrode having a width in the longitudinal direction such that ion packets transit near the at least one detection electrode for a duration that is shorter than the period of the ion packet oscillation. ### Claim 32 (depends on 22) The method of claim 22, wherein the mass analyzer further comprises: an outer electrode coaxial with an inner electrode, the ion packets being caused to oscillate by an electrostatic field between the outer electrode and the inner electrode. ### Claim 33 (depends on 32) The method of claim 32, wherein the step of detecting the pulse transient signal uses at least a part of at least one of: the inner electrode; and the outer electrode, and wherein the pulse transient signal is an image current. ### Claim 34 (depends on 33) The method of claim 33, wherein at least one of: the inner electrode; and outer electrode comprises a first side electrode portion, a second side electrode portion and a central electrode portion located between the first and second side electrode portions and separated therefrom by electrically insulating portions, the step of detecting the pulse transient signal using the central electrode portion. ### Claim 35 (depends on 22) The method of claim 22, wherein the step of detecting the pulse transient signal comprises: detecting a first pulse signal using a first pulse detection electrode; detecting a second pulse signal using a second pulse detection electrode; and determining the pulse transient signal based on the difference between the first pulse signal and the second pulse signal.