EP1220291A2 - Mass spectrometers and methods of mass spectrometry - Google Patents

Mass spectrometers and methods of mass spectrometry Download PDF

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Publication number
EP1220291A2
EP1220291A2 EP01310017A EP01310017A EP1220291A2 EP 1220291 A2 EP1220291 A2 EP 1220291A2 EP 01310017 A EP01310017 A EP 01310017A EP 01310017 A EP01310017 A EP 01310017A EP 1220291 A2 EP1220291 A2 EP 1220291A2
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EP
European Patent Office
Prior art keywords
vacuum chamber
mass spectrometer
electrodes
ion guide
ion
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Granted
Application number
EP01310017A
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German (de)
French (fr)
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EP1220291A3 (en
EP1220291B1 (en
Inventor
Robert Harold Bateman
Kevin Giles
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Micromass UK Ltd
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Micromass UK Ltd
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Publication date
Priority claimed from GBGB0029088.2A external-priority patent/GB0029088D0/en
Priority claimed from GB0110149A external-priority patent/GB0110149D0/en
Priority claimed from GBGB0115504.3A external-priority patent/GB0115504D0/en
Priority claimed from GB0120029A external-priority patent/GB2370685B/en
Application filed by Micromass UK Ltd filed Critical Micromass UK Ltd
Publication of EP1220291A2 publication Critical patent/EP1220291A2/en
Publication of EP1220291A3 publication Critical patent/EP1220291A3/en
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Publication of EP1220291B1 publication Critical patent/EP1220291B1/en
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    • HELECTRICITY
    • H01ELECTRIC ELEMENTS
    • H01JELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00Particle spectrometers or separator tubes
    • H01J49/02Details
    • H01J49/06Electron- or ion-optical arrangements
    • H01J49/062Ion guides
    • H01J49/065Ion guides having stacked electrodes, e.g. ring stack, plate stack

Definitions

  • the present invention relates to mass spectrometers and methods of mass spectrometry.
  • Ion guides comprising rf-only multipole rod sets such as quadrupoles, hexapoles and octopoles are well known.
  • An ion guide comprised of electrodes having apertures may take two main different forms. In a first form all the internal apertures of the electrodes are substantially the same size. Such an arrangement is known as an "ion tunnel". However, a second form referred to as an “ion funnel” is known wherein the electrodes have internal apertures which become progressively smaller in size. Both forms are intended to fall within the scope of the present invention.
  • the apertured electrodes in either case may comprise ring or annular electrodes.
  • the inner circumference of the electrodes is preferably substantially circular. However, the outer circumference of the electrodes does not need to be circular and embodiments of the present invention are contemplated wherein the outer profile of the electrodes takes on other shapes.
  • the preferred embodiment of the present invention uses an ion tunnel ion guide and it has been found that an ion tunnel ion guide exhibits an approximately 25-75% improvement in ion transmission efficiency compared with a conventional multipole, e.g. hexapole, ion guide of comparable length.
  • a conventional multipole e.g. hexapole
  • ion guide of comparable length.
  • the reasons for this enhanced ion transmission efficiency are not fully understood, but it is thought that the ion tunnel may have a greater acceptance angle and a greater acceptance area than a comparable multipole rod set ion guide.
  • one advantage of the preferred embodiment is an improvement in ion transmission efficiency.
  • the inter-vacuum chamber ion guide may comprise an ion funnel.
  • a dc potential gradient is applied along the length of the ion funnel in order to urge ions through the progressively smaller internal apertures of the electrodes.
  • the ion funnel is believed however to suffer from a narrow mass to charge ratio bandpass transmission efficiency. Such problems are not found when using an ion tunnel ion guide.
  • ion optical devices including multipole rod sets, Einzel lenses, segmented multipoles, short (solid) quadrupole pre/post filter lenses ("stubbies"), 3D quadrupole ion traps comprising a central doughnut shaped electrode together with two concave end cap electrodes, and linear (2D) quadrupole ion traps comprising a multipole rod set with entrance and exit ring electrodes.
  • stubbies segmented multipoles
  • 3D quadrupole ion traps comprising a central doughnut shaped electrode together with two concave end cap electrodes
  • 2D linear quadrupole ion traps comprising a multipole rod set with entrance and exit ring electrodes
  • one of the electrodes forming the ion guide may form or constitute a differential pumping aperture between two vacuum chambers.
  • Such an arrangement is particularly advantageous since it allows the interchamber orifice to be much smaller than that which would be provided if a multipole rod set ion guide were used. A smaller interchamber orifice allows the vacuum pumps pumping each vacuum chamber to operate more efficiently.
  • the electrode forming the differential pumping aperture may either have an internal aperture of different size (e.g. smaller) than the other electrodes forming the ion guide or may have the same sized internal aperture.
  • the electrode forming the differential pumping aperture and/or the other electrodes may have an internal diameter selected from the group comprising: (i) 0.5-1.5 mm; (ii) 1.5-2.5 mm; (iii) 2.5-3.5 mm; (iv) 3.5-4.5 mm; (v) 4.5-5.5 mm; (vi) 5.5-6.5 mm; (vii) 6.5-7.5 mm; (viii) 7.5-8.5 mm; (ix) 8.5-9.5 mm; (x) 9.5-10.5 mm; (xi) ⁇ 10.0 mm; (xii) ⁇ 9.0 mm; (xiii) ⁇ 8.0 mm; (xiv) ⁇ 7.0 mm; (xv) 6.0 mm; (xvi) ⁇ 5.0 mm; (xvii) ⁇
  • the differential pumping aperture may have an area selected from the group comprising: (i) ⁇ 40 mm 2 ; (ii) ⁇ 35 mm 2 ; (iii) ⁇ 30 mm 2 ; (iv) ⁇ 25 mm 2 ; (v) ⁇ 20 mm 2 ; (vi) ⁇ 15 mm 2 ; (vii) ⁇ 10 mm 2 ; and (viii) ⁇ 5 mm 2 .
  • the area of the differential pumping aperture may therefore be more than an order of magnitude smaller than the area of the differential pumping aperture inherent with using a multipole ion guide to extend between two vacuum regions.
  • the ion guide may comprise at least 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 electrodes. At least 90%, preferably 100% of the electrodes may be arranged and adapted to be maintained at substantially the same dc reference potential upon which an AC voltage is superimposed.
  • the pressure in the upstream vacuum chamber may, preferably, be: (i) ⁇ 0.5 mbar; (ii) ⁇ 0.7 mbar; (iii) ⁇ 1.0 mbar; (iv) ⁇ 1.3 mbar; (v) ⁇ 1.5 mbar; (vi) ⁇ 2.0 mbar; (vii) ⁇ 5.0 mbar; (viii) ⁇ 10.0 mbar; (ix) 1-5 mbar; (x) 1-2 mbar; or (xi) 0.5-1.5 mbar.
  • the pressure is less than 30 mbar and further preferably less than 20 mbar.
  • the pressure in the downstream vacuum chamber may, preferably, be: (i) 10 -3 -10 -2 mbar; (ii) ⁇ 2 x 10 -3 mbar; (iii) ⁇ 5 x 10 -3 mbar; (iv) ⁇ 10 -2 mbar; (v) 10 -3 -5 x 10 -3 mbar; or (vi) 5 x 10 -3 -10 -2 mbar.
  • At least a majority, preferably all, of the electrodes forming the ion guide may have apertures having internal diameters or dimensions: (i) ⁇ 5.0 mm; (ii) ⁇ 4.5 mm; (iii) ⁇ 4.0 mm; (iv) ⁇ 3.5 mm; (v) ⁇ 3.0 mm; (vi) ⁇ 2.5 mm; (vii) 3.0 ⁇ 0.5 mm; (viii) ⁇ 10.0 mm; (ix) ⁇ 9.0 mm; (x) ⁇ 8.0 mm; (xi) ⁇ 7.0 mm; (xii) ⁇ 6.0 mm; (xiii) 5.0 ⁇ 0.5 mm; or (xiv) 4-6 mm.
  • the length of the ion guide may be: (i) ⁇ 100 mm; (ii) ⁇ 120 mm; (iii) ⁇ 150 mm; (iv) 130 ⁇ 10 mm; (v) 100-150 mm; (vi) ⁇ 160 mm; (vii) ⁇ 180 mm; (viii) ⁇ 200 mm; (ix) 130-150 mm; (x) 120-180 mm; (xi) 120-140 mm; (xii) 130 mm ⁇ 5, 10, 15, 20, 25 or 30 mm; (xiii) 50-300 mm; (xiv) 150-300 mm; (xv) ⁇ 50 mm; (xvi) 50-100 mm; (xvii) 60-90 mm; (xviii) ⁇ 75 mm; (xix) 50-75 mm; (xx) 75-100 mm; (xxi) approx. 26 cm; (xxii) 24-28 cm; (xxiii) 20-30 cm; or (xxiv
  • the ion source is an atmospheric pressure ion source such as an Electrospray (“ES”) ion source or an Atmospheric Pressure Chemical Ionisation (“APCI”) ion source.
  • the ion source may be a Matrix Assisted Laser Desorption Ionisation (“MALDI”) ion source or an Inductively Coupled Plasma (“ICP”) ion source.
  • the MALDI ion source may be either an atmospheric source or a low vacuum source.
  • the ion source is a continuous ion source.
  • the mass spectrometer preferably comprises either a time-of-flight mass analyser, preferably an orthogonal time of flight mass analyser, a quadrupole mass analyser or a quadrupole ion trap.
  • an electrode of the ion guide forms a differential pumping aperture between the input and intermediate vacuum chambers.
  • the mass spectrometer comprises means for supplying an AC-voltage to the electrodes.
  • an AC generator is provided which is connected to the electrodes in such a way that at any instant during an AC cycle of the output of the AC generator, adjacent ones of the electrodes forming the AC-only ion guide are supplied respectively with approximately equal positive and negative potentials relative to a reference potential.
  • the AC power supply may be an RF power supply.
  • the present invention is not intended to be limited to RF frequencies.
  • AC is intended to mean simply that the waveform alternates and hence embodiments of the present invention are also contemplated wherein non-sinusoidal waveforms including square waves are supplied to the ion guide.
  • At least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 or 100 of the electrodes are disposed in one or both vacuum chambers.
  • a differential pumping aperture between the vacuum chambers is formed by an electrode of the ion guide, the differential pumping aperture having an area ⁇ 20 mm 2 , preferably ⁇ 15 mm 2 , further preferably ⁇ 10 mm 2 .
  • a mass spectrometer as claimed in claim 33.
  • a substantially continuous ion tunnel ion guide may be provided which extends through two, three, four or more vacuum chambers. Also, instead of each vacuum chamber being separately pumped, a single split flow vacuum pump may preferably be used to pump each chamber.
  • an ion tunnel 15 comprises a plurality of electrodes 15a,15b having apertures. Adjacent electrodes 15a,15b are connected to different phases of an AC power supply which may in one embodiment be an RF power supply.
  • the first, third, fifth etc. electrodes 15a may be connected to the 0° phase supply 16a
  • the second, fourth, sixth etc. electrodes 15b may be connected to the 180° phase supply 16b.
  • Ions from an ion source pass through the ion tunnel 15 and are efficiently transmitted by it.
  • preferably all of the electrodes 15a,15b are maintained at substantially the same dc reference potential about which an AC voltage is superimposed. Unlike ion traps, blocking dc potentials are not applied to either the entrance or exit of the ion tunnel 15.
  • Fig. 2 shows a preferred embodiment of the present invention.
  • An Electrospray (“ES”) ion source 1 or an Atmospheric Pressure Chemical Ionisation (“APCI”) ion source 1 (which requires a corona pin 2) emits ions which enter a vacuum chamber 17 via a sample cone 3.
  • Vacuum chamber 17 is pumped by a rotary or mechanical pump 4.
  • a portion of the gas and ions pass through a differential pumping aperture 21 with the plate surrounding the aperture being preferably maintained at 50-120V into a vacuum chamber 18 housing an ion tunnel ion guide 15 which extends into another vacuum chamber 19.
  • Vacuum chamber 18 is pumped by a rotary or mechanical pump 7.
  • Ions are transmitted by the ion guide 15 through the vacuum chamber 18 and pass, without exiting the ion guide 15, through another differential pumping aperture 8 formed by an electrode of the ion tunnel ion guide 15 into vacuum chamber 19 which is pumped by a turbo-molecular pump 10. Ions continue to be transmitted by the ion tunnel ion guide 15 through the vacuum chamber 19. The ions then leave the ion guide 15 and pass through differential pumping aperture 11 into an analyser vacuum chamber 20 which is pumped by a turbo-molecular pump 14.
  • Analyser vacuum chamber 20 houses a prefilter rod set 12, a quadrupole mass filter/analyser 13 and may include other elements such as a collision cell (not shown), another quadrupole mass filter/analyser together with an ion detector (not shown) or a time of flight analyser (not shown).
  • An AC-voltage is applied to the electrodes and the ion tunnel 15 is preferably maintained at 0-2 V dc above the dc potential of the plate forming the differential pumping aperture 11 which is preferably at ground (0 V dc). According to other embodiments, the plate forming the differential pumping aperture 11 may be maintained at other dc potentials.
  • the ion tunnel 15 is preferably about 26 cm long and in one embodiment comprises approximately 170 ring electrodes.
  • Upstream vacuum chamber 18 is preferably maintained at a pressure ⁇ 1 mbar, and downstream vacuum chamber 19 is preferably maintained at a pressure of 10 - 3 -10 -2 mbar.
  • the ion guide 15 is preferably supplied with an AC-voltage at a frequency of between 1-2 MHz. However, according to other embodiments, frequencies of 800kHz-3MHz may be used.
  • the electrodes forming the ion tunnel 15 preferably have circular apertures which preferably have a diameter in the range of 3-5 mm.
  • Electrodes of the ion tunnel in one vacuum chamber have a different peak AC voltage amplitude compared with electrodes of the same ion tunnel which are disposed in another vacuum chamber.
  • the electrodes disposed in chamber 18 may be coupled to the AC power supply 16a,16b via a capacitor but the electrodes disposed in chamber 19 may be directly coupled to the AC power supply 16a,16b. Accordingly, the electrodes disposed in chamber 19 may see a peak AC voltage of 500V, but the electrodes disposed in chamber 18 may see a peak AC voltage of 300V.
  • the electrode which forms the differential pumping aperture 8 may be maintained at the AC voltage of either the electrodes in chamber 18 or the electrodes in chamber 19, or alternatively the electrode may be maintained at a voltage which is different from the other electrodes.

Abstract

A mass spectrometer is disclosed comprising an ion guide 15 which spans two or more vacuum chambers 18,19. The ion guide 15 comprises a plurality of electrodes having apertures. Preferably, one of the electrodes 8 may also form the differential pumping aperture which separates two vacuum chambers 18,19.

Description

  • The present invention relates to mass spectrometers and methods of mass spectrometry.
  • Ion guides comprising rf-only multipole rod sets such as quadrupoles, hexapoles and octopoles are well known.
  • Whitehouse and co-workers have disclosed in WO98/06481 and WO99/62101 an arrangement wherein a multipole rod set ion guide extends between two vacuum chambers. However, as will be appreciated by those skilled in the art, since each rod in a multipole rod set has a typical diameter of around 5 mm, and a space must be provided between opposed rods in order for there to be an ion guiding region, then the interchamber aperture when using such an arrangement is correspondingly very large (i.e. > 15 mm in diameter) with a corresponding cross sectional area > 150 mm2. Such large interchamber apertures drastically reduce the effectiveness of the vacuum pumps which are most effective when the interchamber orifice is as small as possible (i.e. only a few millimetres in diameter).
  • It is therefore desired to provide an improved interchamber ion guide.
  • According to a first aspect of the present invention, there is provided a mass spectrometer as claimed in claim 1.
  • Conventional arrangements typically provide two discrete multipole ion guides in adjacent vacuum chambers with a differential pumping aperture therebetween. Such an arrangement suffers from a disruption to the rf field near the end of a multipole rod set and other end effects. However, according to the preferred embodiment of the present invention, the ions do not leave the ion guide as they pass from one vacuum chamber to another. Accordingly, end effect problems are effectively eliminated thereby resulting in improved ion transmission.
  • An ion guide comprised of electrodes having apertures may take two main different forms. In a first form all the internal apertures of the electrodes are substantially the same size. Such an arrangement is known as an "ion tunnel". However, a second form referred to as an "ion funnel" is known wherein the electrodes have internal apertures which become progressively smaller in size. Both forms are intended to fall within the scope of the present invention. The apertured electrodes in either case may comprise ring or annular electrodes. The inner circumference of the electrodes is preferably substantially circular. However, the outer circumference of the electrodes does not need to be circular and embodiments of the present invention are contemplated wherein the outer profile of the electrodes takes on other shapes.
  • The preferred embodiment of the present invention uses an ion tunnel ion guide and it has been found that an ion tunnel ion guide exhibits an approximately 25-75% improvement in ion transmission efficiency compared with a conventional multipole, e.g. hexapole, ion guide of comparable length. The reasons for this enhanced ion transmission efficiency are not fully understood, but it is thought that the ion tunnel may have a greater acceptance angle and a greater acceptance area than a comparable multipole rod set ion guide.
  • Accordingly, one advantage of the preferred embodiment is an improvement in ion transmission efficiency.
  • Although an ion tunnel ion guide is preferred, according to a less preferred embodiment, the inter-vacuum chamber ion guide may comprise an ion funnel. In order to act as an ion guide, a dc potential gradient is applied along the length of the ion funnel in order to urge ions through the progressively smaller internal apertures of the electrodes. The ion funnel is believed however to suffer from a narrow mass to charge ratio bandpass transmission efficiency. Such problems are not found when using an ion tunnel ion guide.
  • Various types of other ion optical devices are also known including multipole rod sets, Einzel lenses, segmented multipoles, short (solid) quadrupole pre/post filter lenses ("stubbies"), 3D quadrupole ion traps comprising a central doughnut shaped electrode together with two concave end cap electrodes, and linear (2D) quadrupole ion traps comprising a multipole rod set with entrance and exit ring electrodes. However, such devices are not intended to fall within the scope of the present invention.
  • According to a particularly preferred feature of the present invention, one of the electrodes forming the ion guide may form or constitute a differential pumping aperture between two vacuum chambers. Such an arrangement is particularly advantageous since it allows the interchamber orifice to be much smaller than that which would be provided if a multipole rod set ion guide were used. A smaller interchamber orifice allows the vacuum pumps pumping each vacuum chamber to operate more efficiently.
  • The electrode forming the differential pumping aperture may either have an internal aperture of different size (e.g. smaller) than the other electrodes forming the ion guide or may have the same sized internal aperture. The electrode forming the differential pumping aperture and/or the other electrodes may have an internal diameter selected from the group comprising: (i) 0.5-1.5 mm; (ii) 1.5-2.5 mm; (iii) 2.5-3.5 mm; (iv) 3.5-4.5 mm; (v) 4.5-5.5 mm; (vi) 5.5-6.5 mm; (vii) 6.5-7.5 mm; (viii) 7.5-8.5 mm; (ix) 8.5-9.5 mm; (x) 9.5-10.5 mm; (xi) ≤ 10.0 mm; (xii) ≤ 9.0 mm; (xiii) ≤ 8.0 mm; (xiv) ≤ 7.0 mm; (xv) ≤ 6.0 mm; (xvi) ≤ 5.0 mm; (xvii) ≤ 4.0 mm; (xviii) ≤ 3.0 mm; (xix) ≤ 2.0 mm; (xx) ≤ 1.0 mm; (xxi) 0-2 mm; (xxii) 2-4 mm; (xxiii) 4-6 mm; (xxiv) 6-8 mm; and (xxv) 8-10 mm.
  • The differential pumping aperture may have an area selected from the group comprising: (i) ≤ 40 mm2; (ii) ≤ 35 mm2; (iii) ≤ 30 mm2; (iv) ≤ 25 mm2; (v) ≤ 20 mm2; (vi) ≤ 15 mm2; (vii) ≤ 10 mm2; and (viii) ≤ 5 mm2. The area of the differential pumping aperture may therefore be more than an order of magnitude smaller than the area of the differential pumping aperture inherent with using a multipole ion guide to extend between two vacuum regions.
  • The ion guide may comprise at least 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 electrodes. At least 90%, preferably 100% of the electrodes may be arranged and adapted to be maintained at substantially the same dc reference potential upon which an AC voltage is superimposed.
  • According to the preferred embodiment, when the ion guide extends between two vacuum chambers, the pressure in the upstream vacuum chamber may, preferably, be: (i) ≥ 0.5 mbar; (ii) ≥ 0.7 mbar; (iii) ≥ 1.0 mbar; (iv) ≥ 1.3 mbar; (v) ≥ 1.5 mbar; (vi) ≥ 2.0 mbar; (vii) ≥ 5.0 mbar; (viii) ≥ 10.0 mbar; (ix) 1-5 mbar; (x) 1-2 mbar; or (xi) 0.5-1.5 mbar. Preferably, the pressure is less than 30 mbar and further preferably less than 20 mbar. The pressure in the downstream vacuum chamber may, preferably, be: (i) 10-3-10-2 mbar; (ii) ≥ 2 x 10-3 mbar; (iii) ≥ 5 x 10-3 mbar; (iv) ≤ 10-2 mbar; (v) 10-3-5 x 10-3 mbar; or (vi) 5 x 10-3-10-2 mbar.
  • At least a majority, preferably all, of the electrodes forming the ion guide may have apertures having internal diameters or dimensions: (i) ≤ 5.0 mm; (ii) ≤ 4.5 mm; (iii) ≤ 4.0 mm; (iv) ≤ 3.5 mm; (v) ≤ 3.0 mm; (vi) ≤ 2.5 mm; (vii) 3.0 ± 0.5 mm; (viii) ≤ 10.0 mm; (ix) ≤ 9.0 mm; (x) ≤ 8.0 mm; (xi) ≤ 7.0 mm; (xii) ≤ 6.0 mm; (xiii) 5.0 ± 0.5 mm; or (xiv) 4-6 mm.
  • The length of the ion guide may be: (i) ≥ 100 mm; (ii) ≥ 120 mm; (iii) ≥ 150 mm; (iv) 130 ± 10 mm; (v) 100-150 mm; (vi) ≤ 160 mm; (vii) ≤ 180 mm; (viii) ≤ 200 mm; (ix) 130-150 mm; (x) 120-180 mm; (xi) 120-140 mm; (xii) 130 mm ± 5, 10, 15, 20, 25 or 30 mm; (xiii) 50-300 mm; (xiv) 150-300 mm; (xv) ≥ 50 mm; (xvi) 50-100 mm; (xvii) 60-90 mm; (xviii) ≥ 75 mm; (xix) 50-75 mm; (xx) 75-100 mm; (xxi) approx. 26 cm; (xxii) 24-28 cm; (xxiii) 20-30 cm; or (xxiv) > 30 cm.
  • According to a preferred embodiment, the ion source is an atmospheric pressure ion source such as an Electrospray ("ES") ion source or an Atmospheric Pressure Chemical Ionisation ("APCI") ion source. According to an alternative embodiment, the ion source may be a Matrix Assisted Laser Desorption Ionisation ("MALDI") ion source or an Inductively Coupled Plasma ("ICP") ion source. The MALDI ion source may be either an atmospheric source or a low vacuum source.
  • According to a preferred embodiment, the ion source is a continuous ion source.
  • The mass spectrometer preferably comprises either a time-of-flight mass analyser, preferably an orthogonal time of flight mass analyser, a quadrupole mass analyser or a quadrupole ion trap.
  • According to a second aspect of the present invention, there is provided a mass spectrometer as claimed in claim 21.
  • Preferably, an electrode of the ion guide forms a differential pumping aperture between the input and intermediate vacuum chambers.
  • Preferably, the mass spectrometer comprises means for supplying an AC-voltage to the electrodes. Preferably, an AC generator is provided which is connected to the electrodes in such a way that at any instant during an AC cycle of the output of the AC generator, adjacent ones of the electrodes forming the AC-only ion guide are supplied respectively with approximately equal positive and negative potentials relative to a reference potential.
  • In one embodiment the AC power supply may be an RF power supply. However, the present invention is not intended to be limited to RF frequencies. Furthermore, "AC" is intended to mean simply that the waveform alternates and hence embodiments of the present invention are also contemplated wherein non-sinusoidal waveforms including square waves are supplied to the ion guide.
  • According to a third aspect of the present invention, there is provided a mass spectrometer as claimed in claim 24.
  • Preferably, at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 or 100 of the electrodes are disposed in one or both vacuum chambers.
  • According to a fourth aspect of the present invention, there is provided a mass spectrometer as claimed in claim 29.
  • According to a fifth aspect of the present invention, there is provided a mass spectrometer as claimed in claim 30.
  • Preferably, a differential pumping aperture between the vacuum chambers is formed by an electrode of the ion guide, the differential pumping aperture having an area ≤ 20 mm2, preferably ≤ 15 mm2, further preferably ≤ 10 mm2.
  • According to a sixth aspect of the present invention, there is provided a mass spectrometer as claimed in claim 32.
  • According to a seventh aspect of the present invention, there is provided a mass spectrometer as claimed in claim 33.
  • According to a eighth aspect of the present invention, there is provided a mass spectrometer as claimed in claim 34.
  • According to this embodiment a substantially continuous ion tunnel ion guide may be provided which extends through two, three, four or more vacuum chambers. Also, instead of each vacuum chamber being separately pumped, a single split flow vacuum pump may preferably be used to pump each chamber.
  • According to a ninth aspect of the present invention, there is provided a method of mass spectrometry as claimed in claim 35.
  • According to a tenth aspect of the present invention, there is provided a method of mass spectrometry as claimed in claim 36.
  • According to an eleventh aspect of the present invention, there is provided a mass spectrometer as claimed in claim 37.
  • Various embodiments of the present invention will now be described, by way of example only, and with reference to the accompanying drawings in which:
  • Fig. 1 shows an ion tunnel ion guide; and
  • Fig. 2 shows a preferred arrangement.
  • As shown in Fig. 1, an ion tunnel 15 comprises a plurality of electrodes 15a,15b having apertures. Adjacent electrodes 15a,15b are connected to different phases of an AC power supply which may in one embodiment be an RF power supply. For example, the first, third, fifth etc. electrodes 15a may be connected to the 0° phase supply 16a, and the second, fourth, sixth etc. electrodes 15b may be connected to the 180° phase supply 16b. Ions from an ion source pass through the ion tunnel 15 and are efficiently transmitted by it. In contrast to an ion funnel arrangement, preferably all of the electrodes 15a,15b are maintained at substantially the same dc reference potential about which an AC voltage is superimposed. Unlike ion traps, blocking dc potentials are not applied to either the entrance or exit of the ion tunnel 15.
  • Fig. 2 shows a preferred embodiment of the present invention. An Electrospray ("ES") ion source 1 or an Atmospheric Pressure Chemical Ionisation ("APCI") ion source 1 (which requires a corona pin 2) emits ions which enter a vacuum chamber 17 via a sample cone 3. Vacuum chamber 17 is pumped by a rotary or mechanical pump 4. A portion of the gas and ions pass through a differential pumping aperture 21 with the plate surrounding the aperture being preferably maintained at 50-120V into a vacuum chamber 18 housing an ion tunnel ion guide 15 which extends into another vacuum chamber 19. Vacuum chamber 18 is pumped by a rotary or mechanical pump 7. Ions are transmitted by the ion guide 15 through the vacuum chamber 18 and pass, without exiting the ion guide 15, through another differential pumping aperture 8 formed by an electrode of the ion tunnel ion guide 15 into vacuum chamber 19 which is pumped by a turbo-molecular pump 10. Ions continue to be transmitted by the ion tunnel ion guide 15 through the vacuum chamber 19. The ions then leave the ion guide 15 and pass through differential pumping aperture 11 into an analyser vacuum chamber 20 which is pumped by a turbo-molecular pump 14. Analyser vacuum chamber 20 houses a prefilter rod set 12, a quadrupole mass filter/analyser 13 and may include other elements such as a collision cell (not shown), another quadrupole mass filter/analyser together with an ion detector (not shown) or a time of flight analyser (not shown).
  • An AC-voltage is applied to the electrodes and the ion tunnel 15 is preferably maintained at 0-2 V dc above the dc potential of the plate forming the differential pumping aperture 11 which is preferably at ground (0 V dc). According to other embodiments, the plate forming the differential pumping aperture 11 may be maintained at other dc potentials.
  • The ion tunnel 15 is preferably about 26 cm long and in one embodiment comprises approximately 170 ring electrodes. Upstream vacuum chamber 18 is preferably maintained at a pressure ≥ 1 mbar, and downstream vacuum chamber 19 is preferably maintained at a pressure of 10-3-10-2 mbar. The ion guide 15 is preferably supplied with an AC-voltage at a frequency of between 1-2 MHz. However, according to other embodiments, frequencies of 800kHz-3MHz may be used. The electrodes forming the ion tunnel 15 preferably have circular apertures which preferably have a diameter in the range of 3-5 mm.
  • Embodiments of the present invention are also contemplated wherein electrodes of the ion tunnel in one vacuum chamber have a different peak AC voltage amplitude compared with electrodes of the same ion tunnel which are disposed in another vacuum chamber. For example, with reference to Fig. 2 the electrodes disposed in chamber 18 may be coupled to the AC power supply 16a,16b via a capacitor but the electrodes disposed in chamber 19 may be directly coupled to the AC power supply 16a,16b. Accordingly, the electrodes disposed in chamber 19 may see a peak AC voltage of 500V, but the electrodes disposed in chamber 18 may see a peak AC voltage of 300V. The electrode which forms the differential pumping aperture 8 may be maintained at the AC voltage of either the electrodes in chamber 18 or the electrodes in chamber 19, or alternatively the electrode may be maintained at a voltage which is different from the other electrodes.

Claims (41)

  1. A mass spectrometer, comprising:
    an ion source;
    an input vacuum chamber;
    an analyser vacuum chamber comprising an ion mass analyser; and
    an intermediate vacuum chamber, said intermediate vacuum chamber being disposed between said input vacuum chamber and said analyser vacuum chamber; and
    an AC-only ion guide extending between said input vacuum chamber and said intermediate vacuum chamber;
       characterised in that:
    said AC-only ion guide comprises a plurality of electrodes having internal apertures.
  2. A mass spectrometer as claimed in claim 1, wherein at least a majority of said electrodes have substantially similar sized internal apertures.
  3. A mass spectrometer as claimed in claim 1, wherein at least a majority of said electrodes have internal apertures which become progressively smaller.
  4. A mass spectrometer as claimed in claim 1, 2 or 3, wherein an electrode of said ion guide forms a differential pumping aperture between said input and said intermediate vacuum chambers.
  5. A mass spectrometer as claimed in claim 4, wherein the electrode forming said differential pumping aperture has an internal diameter selected from the group comprising: (i) 0.5-1.5 mm; (ii) 1.5-2.5 mm; (iii) 2.5-3.5 mm; (iv) 3.5-4.5 mm; (v) 4.5-5.5 mm; (vi) 5.5-6.5 mm; (vii) 6.5-7.5 mm; (viii) 7.5-8.5 mm; (ix) 8.5-9.5 mm; (x) 9.5-10.5 mm; (xi) ≤ 10.0 mm; (xii) ≤ 9.0 mm; (xiii) ≤ 8.0 mm; (xiv) ≤ 7.0 mm; (xv) ≤ 6.0 mm; (xvi) ≤ 5.0 mm; (xvii) ≤ 4.0 mm; (xviii) ≤ 3.0 mm; (xix) ≤ 2.0 mm; (xx) ≤ 1.0 mm; (xxi) 0-2 mm; (xxii) 2-4 mm; (xxiii) 4-6 mm; (xxiv) 6-8 mm; and (xxv) 8-10 mm.
  6. A mass spectrometer as claimed in claim 4 or 5, wherein at least a majority, preferably all, of the electrodes apart from the electrode forming said differential pumping aperture have internal diameters selected from the group comprising: (i) 0.5-1.5 mm; (ii) 1.5-2.5 mm; (iii) 2.5-3.5 mm; (iv) 3.5-4.5 mm; (v) 4.5-5.5 mm; (vi) 5.5-6.5 mm; (vii) 6.5-7.5 mm; (viii) 7.5-8.5 mm; (ix) 8.5-9.5 mm; (x) 9.5-10.5 mm; (xi) ≤ 10.0 mm; (xii) ≤ 9.0 mm; (xiii) ≤ 8.0 mm; (xiv) ≤ 7.0 mm; (xv) ≤ 6.0 mm; (xvi) ≤ 5.0 mm; (xvii) ≤ 4.0 mm; (xviii) ≤ 3.0 mm; (xix) ≤ 2.0 mm; (xx) ≤ 1.0 mm; (xxi) 0-2 mm; (xxii) 2-4 mm; (xxiii) 4-6 mm; (xxiv) 6-8 mm; and (xxv) 8-10 mm.
  7. A mass spectrometer as claimed in claim 4, wherein the electrode forming said differential pumping aperture has an internal aperture of different size to the other electrodes forming said ion guide.
  8. A mass spectrometer as claimed in claim 7, wherein the electrode forming said differential pumping aperture has a smaller internal aperture than the other electrodes forming said ion guide.
  9. A mass spectrometer as claimed in claim 4, wherein the electrode forming said differential pumping aperture has an internal aperture substantially the same size as the other electrodes forming said ion guide.
  10. A mass spectrometer as claimed in claim 4, wherein said differential pumping aperture has an area selected from the group comprising: (i) ≤ 40 mm2; (ii) ≤ 35 mm2; (iii) ≤ 30 mm2; (iv) ≤ 25 mm2; (v) ≤ 20 mm2; (vi) ≤ 15 mm2; (vii) ≤ 10 mm2; and (viii) ≤ 5 mm2.
  11. A mass spectrometer as claimed in any preceding claim, wherein said ion guide comprises at least 4, 5, 6, 7, 8, 9, 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 electrodes.
  12. A mass spectrometer as claimed in any preceding claim, wherein the pressure in said input vacuum chamber is selected from the group comprising: (i) ≥ 0.5 mbar; (ii) ≥ 0.7 mbar; (iii) ≥ 1.0 mbar; (iv) ≥ 1.3 mbar; (v) ≥ 1.5 mbar; (vi) ≥ 2.0 mbar; (vii) ≥ 5.0 mbar; (viii) ≥ 10.0 mbar; (ix) 1-5 mbar; (x) 1-2 mbar; and (xi) 0.5-1.5 mbar.
  13. A mass spectrometer as claimed in any preceding claim, wherein the pressure in said intermediate vacuum chamber is selected from the group comprising: (i) 10-3-10-2 mbar; (ii) ≥ 2 x 10-3 mbar; (iii) ≥ 5 x 10-3 mbar; (iv) ≤ 10-2 mbar; (v) 10-3-5 x 10-3 mbar; and (vi) 5 x 10-3-10-2 mbar.
  14. A mass spectrometer as claimed in any preceding claim, wherein the length of said ion guide is selected from the group comprising: (i) ≥ 100 mm; (ii) ≥ 120 mm; (iii) ≥ 150 mm; (iv) 130 ± 10 mm; (v) 100-150 mm; (vi) ≤ 160 mm; (vii) ≤ 180 mm; (viii) ≤ 200 mm; (ix) 130-150 mm; (x) 120-180 mm; (xi) 120-140 mm; (xii) 130 mm ± 5, 10, 15, 20, 25 or 30 mm; (xiii) 50-300 mm; (xiv) 150-300 mm; (xv) ≥ 50 mm; (xvi) 50-100 mm; (xvii) 60-90 mm; (xviii) ≥ 75 mm; (xix) 50-75 mm; (xx) 75-100 mm; (xxi) approx. 26 cm; (xxii) 24-28 cm; (xxiii) 20-30 cm; and (xxiv) > 30 cm.
  15. A mass spectrometer as claimed in any preceding claim, wherein said ion source is an atmospheric pressure ion source.
  16. A mass spectrometer as claimed in claim 15, wherein said ion source is an Electrospray ("ES") ion source or an Atmospheric Pressure Chemical Ionisation ("APCI") ion source.
  17. A mass spectrometer as claimed in any of claims 1-14, wherein said ion source is a Matrix Assisted Laser Desorption Ionisation ("MALDI") ion source.
  18. A mass spectrometer as claimed in claim 15, wherein said ion source is an Inductively Coupled Plasma ("ICP") ion source.
  19. A mass spectrometer as claimed in any preceding claim, wherein said mass analyser is selected from the group comprising: (i) a time-of-flight mass analyser, preferably an orthogonal time of flight mass analyser; (ii) a quadrupole mass analyser; and (iii) a quadrupole ion trap.
  20. A mass spectrometer as claimed in any preceding claim, wherein at least 90%, preferably 100% of said plurality of electrodes are arranged to be maintained at substantially the same dc reference potential about which an AC voltage supplied to said electrodes is superimposed.
  21. A mass spectrometer, comprising:
    an input vacuum chamber;
    an analyser vacuum chamber comprising a mass analyser; and
    an intermediate vacuum chamber, said intermediate vacuum chamber being arranged between said input vacuum chamber and said analyser vacuum chamber;
       characterised in that:
    said mass spectrometer further comprises an ion guide comprising at least five electrodes having apertures, said ion guide extending from said input vacuum chamber through to said intermediate vacuum chamber.
  22. A mass spectrometer as claimed in claim 21, wherein an electrode of said ion guide forms a differential pumping aperture between said input vacuum chamber and said intermediate vacuum chamber.
  23. A mass spectrometer as claimed in claim 21 or 22, further comprising means for supplying an AC-voltage to said electrodes.
  24. A mass spectrometer, comprising:
    an inter-vacuum chamber ion guide, said inter-vacuum chamber ion guide being > 5 cm in length;
       characterised in that:
    said ion guide comprises a plurality of electrodes having apertures.
  25. A mass spectrometer as claimed in claim 24, wherein said ion guide comprises at least 10, 20, 30, 40, 50, 60, 70, 80, 90, 100, 110, 120, 130, 140, 150, 160, 170, 180, 190 or 200 electrodes.
  26. A mass spectrometer as claimed in claim 25, wherein at least 5, 10, 15, 20, 25, 30, 35, 40, 45, 50 or 100 of said electrodes are disposed in an input vacuum chamber.
  27. A mass spectrometer as claimed in claim 26, wherein at least 5, 10, 15, 20, 25, 30, 35, 40, 45 or 50 or 100 of said electrodes are disposed in an intermediate vacuum chamber, said intermediate vacuum chamber being arranged between said input vacuum chamber and an analyser vacuum chamber comprising a mass analyser, said input and intermediate vacuum chambers being separated by an inter-chamber differential pumping aperture or orifice.
  28. A mass spectrometer as claimed in claim 27, wherein an electrode of said ion guide forms said inter-chamber aperture or orifice.
  29. A mass spectrometer comprising:
    an ion source selected from the group comprising: (i) an Electrospray ("ES") ion source; (ii) an Atmospheric Pressure Chemical Ionisation ("APCI") ion source; (iii) a Matrix Assisted Laser Desorption Ionisation ("MALDI") ion source; and (iv) an Inductively Coupled Plasma ("ICP") ion source;
    an input vacuum chamber;
    an intermediate vacuum chamber separated from the input vacuum chamber by a differential pumping aperture; and
    a mass analyser, preferably a time of flight or a quadrupole mass analyser disposed in an analyser vacuum chamber; and
    an ion guide spanning said input and intermediate vacuum chambers;
       characterised in that:
    said ion guide comprises ≥ 10 electrodes having apertures with a said electrode forming said differential pumping aperture.
  30. A mass spectrometer comprising:
    an AC-only ion guide comprising a plurality of electrodes having apertures spanning two vacuum chambers, each said vacuum chamber comprising a vacuum pump for pumping gas from said vacuum chamber so as to produce a partial vacuum in said vacuum chamber.
  31. A mass spectrometer as claimed in claim 30, wherein a differential pumping aperture between said vacuum chambers is formed by an electrode of said ion guide, said differential pumping aperture having an area ≤ 20 mm2, preferably ≤ 15 mm2, further preferably ≤ 10 mm2.
  32. A mass spectrometer comprising:
    an input vacuum chamber, said input vacuum chamber including a port connected to a vacuum pump;
    an intermediate vacuum chamber, said intermediate vacuum chamber including a port connected to another vacuum pump; and
    an interchamber orifice or aperture separating said vacuum chambers;
       characterised in that:
    said interchamber orifice is formed by an electrode of an ion guide comprised of a plurality of electrodes having apertures.
  33. A mass spectrometer, comprising:
    an ion source;
    an input vacuum chamber;
    an intermediate vacuum chamber; and
    an AC-only ion guide disposed in said input vacuum chamber and extending beyond said input vacuum chamber into said intermediate vacuum chamber;
       characterised in that:
    said ion guide comprises a plurality of electrodes each having substantially similar internal apertures and wherein at least one electrode of said ion guide forms a differential pumping aperture between said vacuum chambers.
  34. A mass spectrometer comprising:
    at least two, preferably at least three or four, vacuum chambers, said vacuum chambers preferably connected to a split flow turbo vacuum pump; and
    a substantially continuous ion guide extending between said vacuum chambers, said ion guide comprising a plurality of electrodes having apertures.
  35. A method of mass spectrometry, comprising:
    guiding ions from a vacuum chamber to another vacuum chamber by passing said ions through an ion guide extending between the two vacuum chambers, said ion guide comprising a plurality of electrodes having apertures.
  36. A method of mass spectrometry, comprising:
    generating a beam of ions from an ion source;
    passing said ions into an ion guide comprised of a plurality of electrodes having apertures, said ion guide extending between two vacuum chambers;
    guiding the ions along the ion guide so that they pass from a vacuum chamber into another vacuum chamber without leaving said ion guide; and then
    mass analysing at least some of said ions.
  37. A mass spectrometer comprising a substantially continuous ion guide, preferably comprising a plurality of electrodes having apertures, extending through three or more vacuum chambers.
  38. A mass spectrometer as claimed in any of claims 1-20, further comprising an AC power supply for supplying an AC voltage to said electrodes.
  39. A mass spectrometer as claimed in claim 38, wherein electrodes in said input vacuum chamber are arranged to be supplied with an AC voltage having an amplitude and electrodes in said intermediate vacuum chamber are arranged to be supplied with an AC voltage having another different amplitude.
  40. A mass spectrometer as claimed in claim 39, wherein the amplitude of the AC voltage supplied to the electrodes in said input vacuum chamber is smaller than the amplitude of the AC voltage supplied to the electrodes in the intermediate vacuum chamber, preferably at least 100 V smaller.
  41. A mass spectrometer as claimed in claim 39 or 40, wherein the amplitude of the AC voltage supplied to the electrodes in said input vacuum chamber is in the range 200-400 V and/or the amplitude of the AC voltage supplied to the electrodes in said intermediate vacuum chamber is in the range 400-600 V.
EP01310017A 2000-11-29 2001-11-29 Mass spectrometer and method of mass spectrometry Expired - Lifetime EP1220291B1 (en)

Applications Claiming Priority (10)

Application Number Priority Date Filing Date Title
GB0029088 2000-11-29
GBGB0029088.2A GB0029088D0 (en) 2000-11-29 2000-11-29 Ion tunnel
GBGB0109760.9A GB0109760D0 (en) 2000-11-29 2001-04-20 Mass spectrometers and methods of mass spectrometry
GB0109760 2001-04-20
GB0110149A GB0110149D0 (en) 2000-11-29 2001-04-25 Mass spectrometers and methods of mass spectrometry
GB0110149 2001-04-25
GB0115504 2001-06-25
GBGB0115504.3A GB0115504D0 (en) 2000-11-29 2001-06-25 Mass spectrometers and methods of mass spectrometry
GB0120029A GB2370685B (en) 2000-11-29 2001-08-16 Mass spectrometers and methods of mass spectrometry
GB0120029 2001-08-16

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EP1220291A2 true EP1220291A2 (en) 2002-07-03
EP1220291A3 EP1220291A3 (en) 2004-08-25
EP1220291B1 EP1220291B1 (en) 2007-02-28

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ATE355608T1 (en) 2006-03-15
DE60126901T2 (en) 2007-06-14
EP1220291A3 (en) 2004-08-25
DE20122469U1 (en) 2005-11-24
DE60126901D1 (en) 2007-04-12
EP1220291B1 (en) 2007-02-28

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