EP2534670B1 - Elektrodensystem einer linearen ionenfalle - Google Patents

Elektrodensystem einer linearen ionenfalle Download PDF

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Publication number
EP2534670B1
EP2534670B1 EP10787587.4A EP10787587A EP2534670B1 EP 2534670 B1 EP2534670 B1 EP 2534670B1 EP 10787587 A EP10787587 A EP 10787587A EP 2534670 B1 EP2534670 B1 EP 2534670B1
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EP
European Patent Office
Prior art keywords
electrodes
ion
trap
electrode
slit
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Application number
EP10787587.4A
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English (en)
French (fr)
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EP2534670A1 (de
Inventor
Mikhail Yurievich Sudakov
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Shimadzu Corp
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Shimadzu Corp
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/422—Two-dimensional RF ion traps
    • H01J49/4225—Multipole linear ion traps, e.g. quadrupoles, hexapoles
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
    • H01J49/00—Particle spectrometers or separator tubes
    • H01J49/26—Mass spectrometers or separator tubes
    • H01J49/34—Dynamic spectrometers
    • H01J49/42—Stability-of-path spectrometers, e.g. monopole, quadrupole, multipole, farvitrons
    • H01J49/4205—Device types
    • H01J49/422—Two-dimensional RF ion traps
    • H01J49/423—Two-dimensional RF ion traps with radial ejection

Definitions

  • Ion trap can be used directly for mass analysis and also for trapping ion cloud for some time and preparation of ion population for further analysis in downstream mass analyzers.
  • Linear ion traps with trapping field formed by four elongated electrodes (rods) arranged around common axis (trap axis) are known in the art. Shortest distance from the axis to the electrode surface - r 0 is called 'field radius' or the inscribed radius of the trap. This is a major geometrical parameter of the trap. Main difference in the design of linear ion traps lies in the shape of working surfaces of electrodes, i.e. the inner shape of electrodes which define field shape in radial direction. Trapping field in such traps is created by application of radiofrequency potentials RF+ and RF- (further in the text - RF supply), positive phase on one pare of oppositely placed electrodes and negative phase on the other pair correspondingly.
  • RF+ and RF- further in the text - RF supply
  • Amplitude V RF and frequency ⁇ of the RF supply are also main parameters of the ion trap because they define a mass range of trapped ions.
  • Fields created by variable AC potentials are used for manipulations with ion cloud. Positive and negative potentials (AC+ and AC-) are applied to the one pair of oppositely placed electrodes. Falling into resonance with excitation field ions increases amplitude of their vibration and can appear at the electrodes.
  • AC+ and AC- Positive and negative potentials
  • Falling into resonance with excitation field ions increases amplitude of their vibration and can appear at the electrodes.
  • slits are cut parallel to the axis of trap. It is possible to use ejection slits in all four electrodes.
  • Methods of ion manipulations in ion traps are based on resonance excitation of ion vibrations. That is why main (secular) frequency of ion vibrations should be well defined and should depend on ion mass only. In order to achieve this, a returning force of the effective potential of the trap should be linearly proportional to the distance of ion from the trap axis. Only quadrupole fields have such property. In order to create quadrupole fields electrodes of the trap should have hyperbolic shape, because hyperbolas are equipotential surfaces of the quadrupole fields.
  • Patent US 6,797,950 describes a linear ion trap with four extended electrodes arranged symmetrically around longitudinal axis of the trap, each electrode has a hyperbolic shape of working surface. Manufacturing and accurate assembling of hyperbolic electrodes is complicated and expensive process. These problems become even more difficult with miniaturization of ion traps. Presence of ejection slits introduces imperfections to the shape of trapping field, resulting in reduction of electrical field in the vicinity of the slit. Due to this ion traps with hyperbolic electrodes are designed with rather narrow slits - not more than 10% of the inscribed radius.
  • Ion trap described in US 6,838,666 better satisfies requirements of miniaturization and manufacturing. Electrodes of this trap are extended flat plates. At the same time such simplification of design results in significant degradation of the trapping field shape due to significant deviations of the trapping field from quadrupole. It is known that field strength is reduced near flat electrode surfaces, thus use of flat plate electrodes only increases effect of field reduction in the vicinity of ejection slits. Secular frequency of ions becomes dependent not only on ion mass, but also on the amplitude of ion vibrations. While amplitude of ion vibration is increased and ions approach ejection slits, ions fall out of resonance with excitation field. As the result, ions either not ejected through the slit to detector, or ejected after significant time delay, which significantly reduces resolving power of mass analysis.
  • Field shape can be improved to some extend by variation of potential along the surface of flat electrode.
  • Patent application WO 2005/119737 describes a linear ion trap in which flat electrodes are separated into a number of longitudinal strips. RF potential is applied to the strips in certain proportion.
  • Advantage of this trap is that electrodes can be manufactured with the use of printed circuit board technology. With the use of several strips per electrode the shape of trapping field can be rather close to quadrupole. At the same time such solution for the problem results in significant complication of power supply.
  • US 2007/0176098 A1 describes an electrode structure for manipulating ions, said structure including a plurality of electrodes elongated along the z-axis. Each electrode has an outer surface, and at least a section of the outer surface is curved. The cross section is generally hyperbolic to facilitate the utilization of quadrupole ion trapping fields.
  • US 2,989,952 A discloses an arrangement for separating ions having different specific charges with electrode means for creating an electric field in the space between them positioned in an evacuated vessel, whereby adjacent surfaces of said electrode means having e.g. a hyperboloidal shape.
  • a problem which is solved by present invention is improvement of resolving power of mass analyzer with simultaneous simplification of electrode design.
  • Technical result is a compensation of field reduction in the region of ejection slit.
  • Target is achieved by modification of electrode design.
  • the present invention refers to a linear ion trap according to claim 1.
  • Favorable embodiments are described in the dependent claims.
  • the system contains two pairs of electrodes 1. In each pair electrodes are oppositely located. Planes of symmetry of pairs are perpendicular to each other. Each of two electrodes of at least one pair has a cross-section substantially a shape of isosceles triangle with a top directed towards longitudinal axis of the trap. Parameter r 0 in Fig. 1 is a radius of the circle inscribed between electrodes, ⁇ - is an angle between working planes 2 of electrode 1. Angles at the bottom of triangle can be cut, as shown in Fig. 1 , in the rest part working surface is made flat.
  • the shape of electrode cross section 'isosceles triangle' should be understood as a shape of main external contour of the cross section. Inside this contour, i.e.
  • each of two opposed electrodes of pair have longitudinal slit (slit width designated as d) for ejecting ions towards detector, slit is placed at the top of triangle, i.e. in the plane of electrode symmetry.
  • excitation potentials AC+ and AC- are applied between those electrodes.
  • resolving power which equals to the mass of ions to the peak width of the ion current expressed in mass units.
  • Such shape of RF supply is most convenient for implementation of frequency scan by gradual increasing of the signal period. In simulations increase of the square wave period was 50ps after every 20 complete RF cycles.
  • Modelling was performed for singly charged ions of mass 1891Da. For better statistics the ion group consisted of 1000 identical particles. Random distribution of initial locations for ions was in accordance with normal distribution with standard deviation 0.05 mm in both radial directions X and Y, which corresponds to symmetrical ion cloud in the trap centre. Initial period of the square wave RF supply was selected near 2.5 ⁇ s so that resonance ejection of ions happened approximately after 20-30 ms. For modelling of ion collisions with buffer gas a model of hard sphere collisions was used. Helium at pressure of 0.2mTorr was used as a buffer gas. Modelling assumed that fields are independent of axial location along the trap. Such assumption is valid at least for the central part of the trap.
  • FIG. 3A shows a time domain of ion vibration amplitude in the direction of excitation (X) for an ion trap with electrode angles 140°. Approximately at 20 ms ion falls into resonance with excitation field and amplitude of its vibrations starts to grow. Increase of the vibration amplitude is uniform and after another 1.5 ms ion is ejected through the slit in positive X direction, because coordinate of ion becomes bigger than the inscribed radius of the trap (5 mm).
  • Maximum resolving power 6600 is achieved with a slit width of 0.8 mm (or 16% of the inscribed radius) at electrode angle of 140°. It should be mentioned that such resolving power at similar conditions can be achieved in ion traps with hyperbolic electrodes only.
  • Graph of resolving power against electrode angle shows that at higher angles (over 140°) resolving power sharply reduced down to several hundred, while at smaller angles the resolution is gradually reduced down to 2000 at angle 130°.
  • resolving power 2000 not so high, it is still two times higher than maximum resolution which can be achieved in ion traps with flat electrodes. Consequently the range of angles from 140° to 130° is of practical interest.
  • the resolving power of a trap is defined by configuration of the electrical fields created by trap electrodes. Later is not changed when dimensions of the trap are proportionally reduced or increased. That is why, although modelling has been done for an ion trap with the inscribed radius of 5 mm, the quality of ion trap operation will not degrade if ion trap of different inscribed radius is used, suggesting that all other dimensions are proportionally changed. That is why we may state that region of angles shown in Fig.6 will be identical for ion traps of geometry described in this invention if slit width equals corresponding part of the inscribed radius. So upper range of slit width 1.2 mm in Fig. 6 corresponds to 24% of the inscribed radius.
  • Fig. 7 shows cross sectional view of the central part of the trap with triangular electrodes in X direction and simple flat electrodes in Y direction.
  • Optimum electrode angles for this trap can be defined by methods described above. Thus this geometry falls into a 'family' of traps described in present invention.
  • electrode system for a linear ion trap allows achieving high resolving power which is comparable with resolution of ion traps of hyperbolic geometry, i.e. significantly higher than can be achieved by prototype ion traps.
  • the working surface of electrodes in proposed system is composed of flat surfaces, which are placed at certain angle to each other, with top of angle directed towards ion trap axis. Manufacturing of such electrodes is much simpler. Angle in the region of ejection slit compensates for local reduction of the field strength.

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  • Chemical & Material Sciences (AREA)
  • Analytical Chemistry (AREA)
  • Electron Tubes For Measurement (AREA)
  • Other Investigation Or Analysis Of Materials By Electrical Means (AREA)
  • Electrostatic Separation (AREA)

Claims (2)

  1. Lineare Ionenfalle, umfassend ein Elektrodensystem mit vier Elektroden (1), die paarweise gegenüberliegend angeordnet sind, wobei Symmetrieebenen von Paaren sich orthogonal zueinander befinden,
    wobei jede Elektrode (1) von mindestens einem Paar im Querschnitt die Form eines gleichschenkligen Dreiecks aufweist, mit
    - einer Spitze, die in Richtung einer Längsachse der Falle gerichtet ist, und
    - flache (Arbeits-)flächen (2),
    wobei ein Winkel zwischen den flachen (Arbeits-)flächen (2) des Dreiecks der Elektroden (1) in einem Bereich von 130° bis 152 Grad liegt,
    wobei die Elektroden (1) entweder ohne einen Schlitz versehen sind und der Winkel zwischen den flachen Oberflächen (2) des Elektrodendreiecks (1) 152 Grad beträgt, oder
    wobei jede Elektrode (1) einen Schlitz zum Ausstoßen von Ionen aufweist, der Schlitz in einer Elektrodensymmetrieebene angeordnet ist und die Breite des Schlitzes nicht größer als 24% des umschriebenen Radius der Falle ist,
    wobei die Winkelwerte so gewählt sind, um das Auflösungsvermögen für die entsprechende Schlitzbreite zu maximieren.
  2. Lineare Ionenfalle nach Anspruch 1, wobei ein Anregungssignal zwischen den Elektroden (1) des Elektrodenpaares angelegt wird, die im Querschnitt im Wesentlichen die Form eines gleichschenkligen Dreiecks aufweisen, um bei Ionen Resonanzanregung zu bewirken.
EP10787587.4A 2010-02-11 2010-09-06 Elektrodensystem einer linearen ionenfalle Active EP2534670B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2010104792/07A RU2466475C2 (ru) 2010-02-11 2010-02-11 Система электродов линейной ионной ловушки
PCT/RU2010/000494 WO2011099889A1 (en) 2010-02-11 2010-09-06 Electrode system of a linear ion trap

Publications (2)

Publication Number Publication Date
EP2534670A1 EP2534670A1 (de) 2012-12-19
EP2534670B1 true EP2534670B1 (de) 2018-07-25

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EP (1) EP2534670B1 (de)
CN (1) CN102754182B (de)
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Publication number Priority date Publication date Assignee Title
CN103714878B (zh) * 2014-01-15 2016-06-08 中国科学院武汉物理与数学研究所 一种集成一体化的离子囚禁装置
CN103903954B (zh) * 2014-03-13 2016-03-30 复旦大学 一种线性离子阱
CN103928288B (zh) * 2014-04-17 2017-01-04 复旦大学 一种用于离子储存与质量分析的三角形圆环离子阱
CN107104032B (zh) * 2017-06-07 2019-04-23 苏州大学 基于非对称三角形电极的线性离子阱、质谱仪及方法
GB201907139D0 (en) * 2019-05-21 2019-07-03 Thermo Fisher Scient Bremen Gmbh Improved electrode arrangement

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US2939952A (en) * 1953-12-24 1960-06-07 Paul Apparatus for separating charged particles of different specific charges

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EP1137046A2 (de) * 2000-03-13 2001-09-26 Agilent Technologies Inc. a Delaware Corporation Herstellung von Hochpräzisionsmultipolen und -filtern
US6797950B2 (en) 2002-02-04 2004-09-28 Thermo Finnegan Llc Two-dimensional quadrupole ion trap operated as a mass spectrometer
US6723986B2 (en) * 2002-03-15 2004-04-20 Agilent Technologies, Inc. Apparatus for manipulation of ions and methods of making apparatus
US6838666B2 (en) 2003-01-10 2005-01-04 Purdue Research Foundation Rectilinear ion trap and mass analyzer system and method
US7034293B2 (en) * 2004-05-26 2006-04-25 Varian, Inc. Linear ion trap apparatus and method utilizing an asymmetrical trapping field
CN1326191C (zh) * 2004-06-04 2007-07-11 复旦大学 用印刷电路板构建的离子阱质量分析仪
EP1930937A4 (de) * 2005-08-30 2010-10-06 Fang Xiang Ionenfalle, mehrfach-elektroden-polsystem und elektrodenpol zur massenspektrometrischen analyse
RU2368980C1 (ru) * 2005-08-30 2009-09-27 Сян ФАН Ионная ловушка, мультипольная электродная система и электрод для масс-спектрометрического анализа
CN1925102A (zh) * 2005-08-30 2007-03-07 方向 优化场形线性离子阱及其质量分析器
US7351965B2 (en) * 2006-01-30 2008-04-01 Varian, Inc. Rotating excitation field in linear ion processing apparatus
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Non-Patent Citations (1)

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Title
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Also Published As

Publication number Publication date
RU2466475C2 (ru) 2012-11-10
RU2010104792A (ru) 2011-08-20
CN102754182B (zh) 2015-08-26
CN102754182A (zh) 2012-10-24
EP2534670A1 (de) 2012-12-19
WO2011099889A1 (en) 2011-08-18

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