WO2013107060A1 - Ion guide device - Google Patents

Ion guide device Download PDF

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Publication number
WO2013107060A1
WO2013107060A1 PCT/CN2012/070709 CN2012070709W WO2013107060A1 WO 2013107060 A1 WO2013107060 A1 WO 2013107060A1 CN 2012070709 W CN2012070709 W CN 2012070709W WO 2013107060 A1 WO2013107060 A1 WO 2013107060A1
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WO
WIPO (PCT)
Prior art keywords
ion
ion guiding
guiding device
filament
layer
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PCT/CN2012/070709
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French (fr)
Chinese (zh)
Inventor
丁力
蒋公羽
孙文剑
Original Assignee
岛津分析技术研发(上海)有限公司
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Application filed by 岛津分析技术研发(上海)有限公司 filed Critical 岛津分析技术研发(上海)有限公司
Priority to PCT/CN2012/070709 priority Critical patent/WO2013107060A1/en
Publication of WO2013107060A1 publication Critical patent/WO2013107060A1/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
    • 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
    • H01J49/066Ion funnels

Definitions

  • the present invention relates to an ion guiding device, particularly an ion guiding device for introducing ions into a lower pressure environment for mass spectrometry in a higher pressure (or lower vacuum) environment.
  • RF radio frequency
  • the effective barrier formed by the voltage causes the ions to accelerate toward the central axis, thereby acting as a convergence. Due to the collision with the neutral gas, the kinetic energy of the ions is lost, and the ions are collected near the central axis, smoothly passing through the differential suction holes, and entering the mass spectrometer in a lower pressure environment.
  • the RF convergence type guiding device is from the multi-pole guiding rod system invented by DJ Douglas (US Pat. No.
  • the position of the electrode of the guiding device or its fixing bracket often inevitably interferes with the gas flow.
  • the influence of the orientation of the pipe on the pumping may cause turbulence, eddy current or airflow jitter in the ion path, which will inevitably affect the ion transmission. .
  • adjacent electrodes to which high-frequency voltages of different phases are applied are not parallel to each other (between lines or between faces), and are concentric arcs with large interelectrode capacitance.
  • US Patent 6107628 The proposed ion funnel uses a sheet electrode with opposite polarity. Due to the multiple stacks, the total capacitance of the electrode structure is large, so that the power consumption of the power supply for which the high frequency voltage is supplied is increased.
  • One of the objects of the present invention is to design a device capable of effectively guiding ions under low vacuum conditions of higher gas pressure and gas flow, which should minimize the adverse effect of the electrode structure of the ion guide on the gas flow, Neutral gas flow has a small blocking effect, and the interelectrode capacitance should be minimized.
  • the rigidity of the filament is poor and it is difficult to accurately fix it at a specific position in the space, so it is necessary to form the filament electrode in a suitable geometric configuration in space and to effectively fix it.
  • the proposed geometric configuration of the filament electrode in space not only satisfies the condition of generating an effective guiding electric field, but also satisfies the condition of the minimum interelectrode capacitance as small as possible.
  • An ion guiding device comprises a plurality of filament electrodes distributed along a guiding axis defining a direction of ion guiding, each layer of filament electrodes comprising at least two distances from said guiding a straightened filament of a certain distance from the shaft, each layer of filament electrodes being rotated about the guiding axis by a certain angle with respect to the adjacent layer of filament electrodes, so that the multilayer filament electrodes are formed to be transparent around the guiding axis
  • the cage ion guiding channel further includes a power supply device that supplies a voltage to each of the layers of filament electrodes to at least configure an electric field that converges ions toward the guiding axis.
  • the plane of each layer of filament electrodes is substantially orthogonal to the guide axis, and the angle ranges from 85 ° to 95. °. In other embodiments of the invention, the angle between the plane in which each of the filament electrodes is located and the guide shaft is allowed to expand to between 70 ° and 110 °.
  • each layer of the filament electrode contains a pair of straightened filaments that are equidistant from the axis of the guide.
  • the direction of each layer of filaments is rotated about the guide axis relative to the direction of the next layer of filaments 90 degrees; the phase of the high frequency voltage applied by each layer of filaments is opposite to the phase of the high frequency voltage of the next layer of filaments.
  • a funnel-type guiding structure in which the distance between the filaments and the guide shaft is gradually reduced is also proposed to facilitate the convergence of ions and the scattering of airflow.
  • N 4, 5 , 6 , 7 , 8 , 9 , 10 , 11 or 12 .
  • a quadrupole field, a hexapole field, an octapole field, or the like can be constructed.
  • the shape of each layer of filament electrodes may be a polygon such as a triangle, a pentagon, or the like.
  • an electric field that converges ions toward the guide axis there are many ways to construct an electric field that converges ions toward the guide axis.
  • a high-frequency voltage having a different phase is supplied to an adjacent layer filament electrode, such as a high-frequency voltage that is opposite to each other, and the high-frequency phase difference is an arc 2 ⁇ /M (M is a natural number greater than 1) Gradually changing high frequency voltage, etc.
  • the amplitude of the high frequency voltage can also vary.
  • a DC voltage is applied to each of the filament electrodes to produce a DC electric field strength that varies along the guide axis within the ion guide channel, the component of which includes an electric field that converges the ions toward the guide axis.
  • the high frequency voltage source includes a plurality of high frequency high voltage switches to generate a rectangular wave high frequency voltage.
  • the guide shaft is not limited to a straight line, but may be a curved guide shaft.
  • the DC voltage supply means may be further included to superimpose a DC voltage between the filaments of at least a portion of the layer of the filament electrodes to assist in deflecting the ions along the guide axis.
  • At least a portion of the ion guiding device has a flowing gas, and the direction of the ion migration caused by the potential gradient in the direction of the guiding axis is opposite to the direction of the axial gas flow, so that only specific ion mobility is achieved. A portion of the ions are efficiently transported.
  • the spacing of the filaments in at least a portion of the layer of filament electrodes and the setting of the high frequency voltage allow ions entering the ion guiding device to achieve mass-selective passage in the vicinity of the space in which the filaments are located. , block or destroy.
  • the setting of the high frequency voltage and the potential gradient setting in the direction of the guiding axis cause the ions entering the ion guiding device to collide with the neutral gas molecules and cause the product ions generated after the collision reaction. , fragment ions, or desolvated ions are efficiently transported.
  • the ion guiding device has a flowing gas, the flowing gas having a gas pressure ranging from 10 to Between 10,000 Pascals.
  • the diameter of the filament is less than 0.5mm to reduce the impact on the airflow.
  • the layers of the filament are fixed on the periphery of the cage guiding channel formed by the filament, that is, the fixing bracket or the fixing is provided at the periphery.
  • venting holes may be provided in the outer wall of the bezel to reduce obstruction to airflow.
  • Embodiments of the present invention also provide an ion guiding device assembly comprising a combination of a plurality of the foregoing ion guiding devices, wherein at least a portion of the ion guiding devices are connected in parallel in a first direction to effect convergence of the guiding axes and / or divergent.
  • At least a portion of the ion guiding devices are connected in series in a second direction to effect engagement of the guiding shaft.
  • FIG. 1 shows a schematic diagram of a straight wire type ion guide according to an embodiment of the present invention.
  • Fig. 2 shows a structure of a straight wire type ion guide according to an embodiment of the present invention.
  • FIG. 3 is a view showing a high-frequency electric field distribution diagram formed by an ion guide according to an embodiment of the present invention.
  • 3(a) is an equipotential line distribution on a section passing through the guide axis
  • FIG. 3(b) is an equipotential line distribution on a section perpendicular to the guide axis.
  • Fig. 4 is a view showing an axial potential distribution formed by an ion guide according to an embodiment of the present invention.
  • Figure 5 shows a simulation of an ion motion trajectory in accordance with an embodiment of the present invention.
  • Fig. 6 shows an example in which the filament electrode is fixed by a cylindrical stent.
  • Fig. 7 shows an example in which the filament electrode is fixed by a cylindrical bracket.
  • Figure 8 shows an embodiment that produces a radial 6-pole field component.
  • Figure 9 shows an embodiment that produces a radial 8-pole field component.
  • Figure 10 illustrates an embodiment that produces a rotating multipole field.
  • FIG 11 shows the manner in which the filaments are tightened by means of elastic pieces.
  • Figure 12 shows the manner in which the filaments are welded and taut by a spring.
  • Figure 13 is a view showing a filament ion guiding device for an arcuate guide shaft according to an embodiment of the present invention.
  • Figure 14 shows a filament ion guiding device for mixing positive and negative ion currents and introducing a collision gas reaction according to an embodiment of the present invention.
  • Figure 15 is a diagram showing an ion guiding device for forming a focusing ability using a spatial periodic direct current potential according to an embodiment of the present invention, wherein four layers are one cycle.
  • Figure 16 is a diagram showing an ion guiding device for forming a focusing ability using a spatial periodic direct current potential according to an embodiment of the present invention, wherein six layers are one cycle.
  • the ion guide proposed by the embodiment of the present invention uses a plurality of layers of straightened filaments to form a space structure similar to the 'Oriental Crown' building of the Shanghai World Expo.
  • This structure has good air permeability and does not block the air flow.
  • a cage channel is formed, and at the periphery of the structure, the 'wire' constituting the channel is tightly fixed to solve the positional stability of the wire and the insulation problem between the wires.
  • the axial direction of the 'filaments' is substantially orthogonal, so the capacitance therebetween can be significantly reduced.
  • the filament electrode has 16
  • the layers, the shapes between the layers are substantially the same.
  • Each layer contains a pair of straightened filaments n.1, n.2 that are equidistant from a guide axis z (n represents the number of layers, in this case 1 to 16) .
  • the second layer of filaments 2.1, 2.2 is perpendicular to the direction of the first layer of filaments 1.1, 1.2. It can also be said that the filament of the second layer is rotated about the guiding axis with respect to the first layer of filaments. Degree.
  • the layers of filaments form a cage guide channel 21 along the guide axis z. All filaments are stretched and secured to the bracket 16.
  • All even layer filaments ie n.1, n.2 n
  • the even-numbered filaments are connected to the phase Y of the output of the high-frequency power source 20 through the capacitor 17, and all the odd-numbered filaments (i.e., n in the n.1, n.2 are odd-numbered filaments)
  • the other phase X (omitted from the figure) connected to the high-frequency power supply by a capacitor, the X and Y phases are opposite in phase.
  • Bracket 16 It can be made of printed circuit boards, or it can be framed with other materials and attached to printed circuit boards.
  • the filament electrodes can be soldered to the pads of the printed circuit board through small holes in the printed circuit board.
  • each layer of filament electrodes essentially uses substantially the same structure, i.e., two parallel filaments.
  • alternative embodiments of the present invention allow the structure of the various layers of filament electrodes to be merely similar, such as in this example, the spacing of the two filaments in each layer can vary.
  • the ion guiding device of the present embodiment is particularly suitable for use in an environment where at least a portion of the device or a surrounding gas is present.
  • the pressure range of the flowing gas is typically 10 to 10,000 Between Pascals.
  • the filaments have a diameter of less than 0.5 mm.
  • the material which can be used as the filament electrode is typically a metal such as a copper wire, a nickel wire, a stainless steel wire or the like.
  • gold may be plated on the surface of the filament.
  • a plurality of voltage dividing resistors 18 may be passed.
  • a direct current potential is applied to each of the filament electrodes.
  • a voltage dividing resistor 18 is connected between each of the filament electrodes.
  • the DC voltage source 19 and the voltage dividing resistor 18 are together in the guiding channel 21
  • An axial potential gradient of DC is formed to facilitate the transport of ions in the axial direction.
  • Figure 3 shows the internal electric field distribution of the ion guiding device shown in Figure 2.
  • Figure 3 (a) Is the equipotential line distribution on the plane between the first layer and the second layer.
  • the electric field distribution in the guiding channel is roughly a quadrupole field. This is essentially different from the electric field in the previous 'ion funnel'.
  • the high frequency quadrupole field has a converging effect on ions throughout the field.
  • the rotationally symmetric high-order field in the 'ion funnel' only plays a 'rebound effect' when the ions are close to the funnel wall.
  • the electric field distribution in the bucket ion guiding device is different from the electric field formed by the conventional quadrupole, as shown in Fig. 3(b).
  • the longitudinal profile of the longitudinal profile is visible.
  • the radial potential distribution is not much different from the potential distribution formed by the quadrupole, but near the filament (potential line 31). Concentric circles)
  • the potential gradient rises abruptly, and ions will be subjected to a large amount of repulsive force in these places, preventing them from escaping from the cage guiding channel.
  • Figure 4 It shows the potential component line distribution of the DC component along the guiding axis when the DC voltage is evenly distributed by the voltage dividing resistor. This potential gradient helps the ions move in the direction of the guiding axis, avoiding long-term retention of ions in the channel. Until the exit 40 Take out and enter the next low pressure environment.
  • Figure 5 is a plot of the ion motion trajectory obtained by computer simulation.
  • the high frequency voltage on the filament is ⁇ 150V ( 0- Peak), frequency is 1MHz, and air pressure is 20torr (2660Pa).
  • the distance between the filament and the guide shaft is 5.25mm at the inlet and is gradually reduced to 1.25mm.
  • the diameter of the filament is 0.2mm, the distance between the two layers of filaments is 1mm.
  • the simulation results show that the mass number is 100 to tens of thousands of monovalent ions, and most of them can enter the outlet orifice 51 through the guiding device.
  • the high frequency voltage applied to the filament electrode is a sinusoidal RF voltage.
  • the high-frequency voltage source can also use a plurality of high-frequency high-voltage switches, and the high-frequency voltage signal generated on the filament electrode is a rectangular wave high-frequency voltage.
  • the holder for fixing the filaments may be formed not only in a rectangular shape as shown in Fig. 1, but also in a cylindrical shape.
  • Figure 6 As shown, a printed circuit 63 and a perforation 64 can be formed in advance on the wall 61 of a hard insulating material such as ceramic.
  • the filament can be embedded on the wall 61, and a plurality of vent holes are formed in the wall. It is convenient for neutral gas to be discharged.
  • the column-shaped brackets shown in Figure 7 can also be used.
  • Columns 71, 72, 73, 74 can be fixed on the cone plate 75, while the filaments 1 , 2 , 3 ... are wound around the column with a pair of columns 71 , 73 and 72 , 74 On.
  • the position of the filaments of this structure is not defined by the holes, but by the diameter at different heights of the columns.
  • the ion guiding device made of the filament can be formed not only in the form of a concentrated high-frequency field mainly for generating a quadrupole field, but also in the form of 6 poles, 8 poles and other multi-pole field-based forms.
  • Figure 8 As shown, the filaments of each layer can be pulled into a triangle with the center of the triangle on the guide shaft. The direction of the next layer of triangular filaments is rotated relative to the direction of the upper layer. Degree.
  • ion guide constructed in accordance with embodiments of the present invention is that it can be rationally selected, blended at the center or periphery for convergence, and combined with ion rebound performance near the filament to accommodate different characteristics of the ion source and gas flow. Guidance requirements under characteristics.
  • the angle of rotation between the guide filaments of each layer remains constant, such as 90 °, 60 °, 45 °, etc.
  • the angle of rotation of each layer of filaments about the guide axis is not necessarily fixed.
  • the angle of rotation of each layer from the second layer of filaments is: 90, 105, 90, 105... degrees; that is, the layer (12.12, 12.2) turns 90 degrees to the layer (11.11, 11.2), and the layer (13.1, 13.2) Level (12.12, 12.2) to 105 Degree.
  • the filaments form a quadrupole field guiding channel that rotates stepwise along the guiding axis.
  • the shape of the ion cloud also rotates during the ion transport, making the transmission channel more uniform in all directions, and may be more suitable for the presence of the swirling airflow.
  • the phase difference of the high frequency voltage between the filaments of each layer may not be 180 degrees. If the phase of the high frequency voltage between the layers is different 120 degrees (or 90 degrees), so that every 3 layers (or 4 layers), the phase of the high-frequency voltage is bypassed for 1 week.
  • This embodiment can be extended to make the high frequency phase difference of adjacent adjacent layers to be arc 2 ⁇ /M , sequentially providing the same frequency M phase high frequency voltage to the 1 to M layer filament electrode, and the M layer continues this phase sequence later, where M is greater than 1 Natural number.
  • an axial traveling wave can be generated to facilitate the ion transmission in the guiding direction.
  • an electric field can be constructed by providing only high frequency voltages of different phase to the adjacent layer filament electrodes, the electric field comprising a component that converges the ions toward the guiding axis.
  • the stress map straightens and tightens the individual filaments.
  • the filament mounting bracket outside the guiding channel should be processed firmly and accurately.
  • Figure 11 The steel column retainer 111 with better elasticity is used in the column design to provide tension, and the slot 112 is used to limit the filament 1 , to fix its axial position.
  • Figure 12 shows a solution for tightening the filaments with elastic tabs.
  • filaments 1 , 3 Waiting through the small holes 122 on the printed circuit board, soldering into the soldering holes 121 on the elastic soldering piece 120, and the elastic soldering pieces are soldered to the conductive circuits of the printed circuit board 123 On. Also shown is a partial refractory member 124 soldered to the same printed circuit board. It means that the circuit board can be used to install these devices as well as leads, connectors, etc., and it is convenient to implement functions such as high-frequency voltage coupling and DC voltage division.
  • the layers of the filament electrodes of each layer are substantially perpendicular to the guide axis.
  • the angle between the plane of each layer of filament electrodes and the guide axis is set at 85 ° to 95 ° Between.
  • the orientation of the filaments is not completely perpendicular to the guiding axis and does not have a serious impact on the ability of the ions to converge.
  • the angle between the plane of the filament and the guide axis is 90 +/- 20 degrees, ie 70 ° -110 °.
  • the guide axis defined by the embodiment of the present invention is not necessarily a straight line, and it may include a curve.
  • Figure 13 shows this curved wire electrode ion guide.
  • Guide axis in the figure 132 For an arc, the ion and neutral gas stream 131 enters the guide channel in a tangential direction from one end of the inlet of the guide shaft.
  • the ions are concentrated near the guiding axis by the concentrated electric field and are led to the exit along the arc of the guiding axis. .
  • the neutral gas flow rushes toward the exhaust port 135 in the original direction.
  • a DC potential difference can be superimposed between 134.2 to further obtain the deflection force of the ions, preventing the ions from being flushed out of the guiding channel by the strong airflow.
  • each layer of filaments can also be formed into a similar pentagon, pentagram or rectangle, or even six or seven sides and above. It will be appreciated that in these embodiments, it is preferred that the layers of filament electrodes remain substantially identical. However, the polygons of the respective filament electrodes are allowed to have similarities in size difference, or slight deformation between the polygons of the respective filament electrodes is allowed.
  • the voltage signals attached to the filaments may also be square waves, sawtooth waves, pulse trains, and may also be a combination of sine waves, square waves and pulse sequences.
  • the alternating voltage signal generating the radially bound electric field does not have to be equally distributed on the layers of filaments, but can be in the same guiding device
  • the spacing of the filaments in at least a portion of the layer of filament electrodes is combined to select ions.
  • Figure 3a For example, the guidance device with a quadrupole RF electric field distribution is described. The influence of the quadrupole electric field on the stability of ion trajectories with different mass-to-charge ratios can be used.
  • the value is roughly inversely proportional to the square of the filament spacing and the mass-to-charge ratio of the ions, and is proportional to the amplitude of the RF voltage attached to the filament.
  • the spacing of the filaments in the bonding structure, through the values of the RC networks 17 and 18 in Fig. 1, static or The RF voltage is dynamically changed, and ions of a selected range of mass-to-charge ratios have q parameters corresponding to stable ion trajectories. Thereby achieving the passage or elimination of the quality of the passing ions.
  • an equivalent barrier can also be generated in the axial direction of the guiding device, and the barrier is also in accordance with the ion mass-to-charge ratio.
  • the change can be used to achieve temporary interception of certain ions.
  • the device can also be used as an ion desolvator to achieve the best ion transport effect through the window through the mass-to-charge ratio dynamic change of the ion mass-to-charge ratio during desolvation.
  • the direct current potential that generates the axial electric field does not have to be equally distributed on the respective layers of filaments.
  • the distribution of the resistor 18 network can be set as needed to change its distribution and change its distribution as needed.
  • a relatively negative DC voltage can be temporarily applied to certain layers to allow ions to be trapped in the areas of these layers during this time. Then, change to a normal gradient distribution to release the trapped ions.
  • Another example is the use of an axial electric field to accelerate ions, or even an alternating axial or transverse electric field to induce high-speed vibration of ions in space, increasing the collision probability and intensity of ions with neutral molecules to achieve ions at high pressure. Under the conditions, it collides with the neutral gas, and then the reaction product ions, ion fragments or desolvated products are effectively guided for analysis.
  • the straight wire electrodes in the guiding device can be made of a resistance heating material.
  • a heating current source device between the two ends of the electric resistance wire, a heating function can be added to the device, and infrared rays can be radiated to generate a pair.
  • a straight wire electrode when the device is operated with a high-frequency alternating current power source, a straight wire electrode can be made of a material having a high magnetic permeability, and the magnetic wire is heated by a magnetic induction eddy current like an induction cooker to achieve the same purpose. Additional heating current source devices can be eliminated.
  • a part of the filaments are shared (as shown in Fig. 14).
  • the combination of 143.1 and 143.2) or the formed guide device can further enhance the ion conduction capability of the device.
  • a plurality of filament ion guiding structures are connected in series, as shown in the figure.
  • the dispersion or convergence and overlap of the plurality of virtual guide axes in the array can be realized, so that a plurality of ion sources and lower ion analysis devices disposed upstream and downstream of the ion guiding structure can realize one-to-many and more For one, many to many ion sources - Analyzer coordination, ie the role of ion current shunts, multiplexers and exchangers.
  • the combination of guides shown in Figure 14 also allows positive ion currents 144, negative ion currents 145, and neutral molecular flows of different polarities. 146
  • the polymerization, mixing and separation are carried out to initiate molecular ion reaction and charge transfer reaction to fragment the target ions, and a separated product ion stream is obtained for subsequent cascade mass spectrometry.
  • the peripheral circuit system can add a DC potential offset that is successively decreasing from left to right between the layers of the guiding system to make the positive ion current 144 is subjected to a guided axial potential distribution 147 that decreases stepwise along the flow direction, while causing the reverse negative ion current 145 to receive a pilot axial potential distribution that rises stepwise along the flow direction.
  • the effect of the inflow into the guiding structure middle section 142 is mixed with each other. Both the positive and negative ion currents in the mid-section of the series guiding structure 142 are directed toward the guiding structure 142 due to the internal alternating quadrupole field.
  • the central axis converges and reacts to obtain the ion fragmentation effect of the so-called charge transfer dissociation (EDD) method.
  • EDD charge transfer dissociation
  • the new positive and negative ion currents obtained after the reaction can pass through the filament groups 142.1 on both sides of the guiding structure
  • the DC deflection potential is further superimposed between 142.2 to deflect and separate to the respective exit channels.
  • the permeability of the filament ion guiding structure can be utilized to guide the structure to the middle section 142
  • a suitable collision gas 146 such as argon, isobutane or the like is introduced to increase the residence time of the positive ion stream 144 and the negative ion stream 145, and can pass the collision gas 146. Catalysts increase the charge transfer efficiency to increase the dissociation effect.
  • each layer here contains a pair of parallel straight filaments n.1, n.2 (n represents the number of layers, and n is a natural number).
  • the second layer of filament 2.1, 2.2 Direction with the first layer of filaments 1.1, 1, 2
  • the direction is perpendicular
  • the filament direction of the third layer is perpendicular to the direction of the second layer of filaments
  • the filament direction of the third layer is parallel to the direction of the first layer of filaments, and so on.
  • the ion can reach a speed of several tens to several hundred meters per second in the axial direction of the ion guide under the action of the airflow and the direct current electric field gradient, at such a speed within a distance of a few millimeters as a refocusing and defocusing unit. Movement is equivalent to the action of a quadrupole field generated by an ion undergoing an alternating voltage of several thousand to several hundreds of thousands of hertz at the same position, thereby achieving focusing of the ions in the radial direction.
  • an equal DC voltage is applied to three adjacent pairs of layers, and the three layers are a group. The voltage between the groups is decremented. The DC electric field generated at this time also causes the ions to move along the axial direction of the guide.

Abstract

An ion guide device consists of multiple layers of filament electrodes (n.1, n.2, n representing the number of layers) straightened and intersecting spatially. The filament electrodes are distributed along a guide shaft z that defines an ion guide direction. Each layer of the filament electrode comprises at least two filaments that are straightened and have a certain distance away from the guide shaft. Each layer of the filament electrode rotates about the guide shaft by a certain angle relative to the adjacent layer of the filament electrode. Therefore, the multiple layers of filament electrodes surround the guide shaft to form a through cage-like ion guide channel (21), and frames (16) for fixing the filaments are arranged at the periphery of the guide channel (21), so that interference of the device on air flows is reduced. A power supply device (19, 20) provides voltage for each layer of the filament electrode, to at least construct an electric field that causes ions to converge to the guide shaft.

Description

离子导引装置  Ion guiding device 技术领域Technical field
本发明涉及一种离子导引装置,尤其是在较高气压(或较低真空度)环境将离子引入较低气压环境进行质谱分析的离子导引装置。 The present invention relates to an ion guiding device, particularly an ion guiding device for introducing ions into a lower pressure environment for mass spectrometry in a higher pressure (or lower vacuum) environment.
背景技术Background technique
在质谱仪中,为了在较高的气压下( 1~104Pa )将离子从离子源引向分析器,通常采用高频(或射频)导引装置,装置中的电极上所加高频电压形成的有效势垒,致使离子向中心轴加速,从而起到一种会聚作用。由于与中性气体的碰撞,离子的动能损失,离子就被聚集在中轴附近,顺利通过差分抽气小孔,进入较低气压环境中的质谱分析装置。这种射频会聚型导引装置从最初D. J. Douglas 发明的的多极导引杆系(美国专利 5179278 )到 R D Smith 提出的离子漏斗(美国专利 6107628 ),到美国专利 6462338B1 , N. Inatsugu , H. Waki 发明的 Q- 阵列导引器;以及 Bateman 等提出的(美国专利 7095013 )行波导引装置,经历了多种变形。然而作为离子源后的第一级导引透镜,伴随着离子进入低压强区的强气流对离子运动起到了关键的作用,甚至气流对离子的作用有时要大于电场对离子的作用。导引装置的电极,或其固定支架的位置往往不可避免地干扰气体流动,加之管路的方位对抽气的影响,有可能在离子路径上造成湍流、涡流或气流抖动,势必影响离子的传输。In mass spectrometers, in order to direct ions from the ion source to the analyzer at higher gas pressures (1~10 4 Pa), high frequency (or RF) guiding devices are usually used, and high frequencies are applied to the electrodes in the device. The effective barrier formed by the voltage causes the ions to accelerate toward the central axis, thereby acting as a convergence. Due to the collision with the neutral gas, the kinetic energy of the ions is lost, and the ions are collected near the central axis, smoothly passing through the differential suction holes, and entering the mass spectrometer in a lower pressure environment. The RF convergence type guiding device is from the multi-pole guiding rod system invented by DJ Douglas (US Pat. No. 5,179,278) to the ion funnel proposed by RD Smith (U.S. Patent No. 6,107,628), to U.S. Patent No. 6,462,338 B1, N. Inatsugu, H. The Q-array introducer invented by Waki; and the traveling wave guiding device proposed by Bateman et al. (US Pat. No. 70,950,013) have undergone various variations. However, as the first-stage guiding lens after the ion source, the strong airflow accompanying the ions entering the low-pressure strong region plays a key role in the ion motion, and even the effect of the airflow on the ions is sometimes greater than the effect of the electric field on the ions. The position of the electrode of the guiding device or its fixing bracket often inevitably interferes with the gas flow. In addition, the influence of the orientation of the pipe on the pumping may cause turbulence, eddy current or airflow jitter in the ion path, which will inevitably affect the ion transmission. .
在美国专利 5572035 中,发明人 Franzen 曾提出用丝网电极构成离子反射面来规矩离子的行程,这种反射面理论上可具有良好的气流通透性。但一般丝网质地较软,发明人没有给出一个如何将其牢固地安装于空间特定位置,而不受气流吹动的方案。如果用附加支架的办法安装,附加支架同样也会影响气流的方向。 In U.S. Patent 5,572,035, the inventor Franzen It has been proposed to use a screen electrode to form an ion reflecting surface to align the stroke of the ion, which theoretically has good airflow permeability. However, in general, the texture of the screen is relatively soft, and the inventors have not given a solution for how to securely mount it in a specific position in space without being blown by air. If the bracket is installed, the additional bracket will also affect the direction of the airflow.
并且,以往的各种离子导引装置中,施加不同相位高频电压的相邻电极不是相互平行(线之间或面之间),就是呈同心圆弧状,极间电容较大。例如美国专利 6107628 提出的离子漏斗使用了加相反极性的薄片电极,由于多组层叠,电极结构的总电容较大,使得为其提供高频电压的电源功耗上升。 Further, in various conventional ion guiding devices, adjacent electrodes to which high-frequency voltages of different phases are applied are not parallel to each other (between lines or between faces), and are concentric arcs with large interelectrode capacitance. For example, US Patent 6107628 The proposed ion funnel uses a sheet electrode with opposite polarity. Due to the multiple stacks, the total capacitance of the electrode structure is large, so that the power consumption of the power supply for which the high frequency voltage is supplied is increased.
加之有很多这样的电极排列在一起,对高频电源来说呈并联,很大的总电容使高频电源功耗加大。 In addition, there are many such electrodes arranged in parallel, which are parallel to the high frequency power supply, and the large total capacitance increases the power consumption of the high frequency power supply.
发明内容Summary of the invention
本发明的目的之一是设计一种能在较高气压和气流的低真空条件下有效地导引离子的装置,该装置应尽可能减少离子导引器的电极结构对气流的不良影响,对中性气体流有很小的阻挡作用,还应尽量降低极间电容。One of the objects of the present invention is to design a device capable of effectively guiding ions under low vacuum conditions of higher gas pressure and gas flow, which should minimize the adverse effect of the electrode structure of the ion guide on the gas flow, Neutral gas flow has a small blocking effect, and the interelectrode capacitance should be minimized.
为了减少电极结构对气流的影响,提出了使用细丝电极产生所需的离子导引电场。然而细丝的刚性较差,难以精准地在空间的特定位置固定下来,因此需要将这种细丝电极在空间形成适当几何构型并有效地固定下来。另外,所提出的细丝电极在空间形成的几何构型,不但要满足产生有效导引电场的条件,还要满足尽量小的极间电容的条件。In order to reduce the influence of the electrode structure on the gas flow, it is proposed to use a filament electrode to generate a desired ion guiding electric field. However, the rigidity of the filament is poor and it is difficult to accurately fix it at a specific position in the space, so it is necessary to form the filament electrode in a suitable geometric configuration in space and to effectively fix it. In addition, the proposed geometric configuration of the filament electrode in space not only satisfies the condition of generating an effective guiding electric field, but also satisfies the condition of the minimum interelectrode capacitance as small as possible.
本发明的一个方面所提出的一种离子导引装置,包含沿着一定义离子导引方向的导引轴分布的多层细丝电极,每层细丝电极包含至少两根距所述导引轴一定距离的、拉直的细丝,每层细丝电极相对于相邻层细丝电极绕所述导引轴旋转一定的角度,使多层细丝电极围绕所述导引轴形成通透的笼状离子导引通道。该离子导引装置还包含电源装置,向各层细丝电极提供电压,以至少构造使离子向所述导引轴会聚的电场。An ion guiding device according to an aspect of the invention comprises a plurality of filament electrodes distributed along a guiding axis defining a direction of ion guiding, each layer of filament electrodes comprising at least two distances from said guiding a straightened filament of a certain distance from the shaft, each layer of filament electrodes being rotated about the guiding axis by a certain angle with respect to the adjacent layer of filament electrodes, so that the multilayer filament electrodes are formed to be transparent around the guiding axis The cage ion guiding channel. The ion guiding device further includes a power supply device that supplies a voltage to each of the layers of filament electrodes to at least configure an electric field that converges ions toward the guiding axis.
作为本发明的优选实施例,每层细丝电极所在的平面与所述导引轴基本正交,其夹角范围为 85 °至 95 °。在本发明的其他实施例中,允许每层细丝电极所在的平面与所述导引轴的夹角扩大至介于 70 °至 110 °之间。As a preferred embodiment of the present invention, the plane of each layer of filament electrodes is substantially orthogonal to the guide axis, and the angle ranges from 85 ° to 95. °. In other embodiments of the invention, the angle between the plane in which each of the filament electrodes is located and the guide shaft is allowed to expand to between 70 ° and 110 °.
作为一种实施方案,还提出了细丝电极的每一层都含有一对与导引轴线等距离的、相互平行的拉直的细丝。每层细丝的方向相对于下一层细丝的方向,绕导引轴旋转 90 度;每层细丝所施加的高频电压相位相对于下一层细丝的高频电压相位相反。 As an embodiment, it is also proposed that each layer of the filament electrode contains a pair of straightened filaments that are equidistant from the axis of the guide. The direction of each layer of filaments is rotated about the guide axis relative to the direction of the next layer of filaments 90 degrees; the phase of the high frequency voltage applied by each layer of filaments is opposite to the phase of the high frequency voltage of the next layer of filaments.
作为本发明的优选实施例,还提出了每层细丝与导引轴距离逐渐缩小的漏斗型导引结构,以利于离子的会聚和气流的散开。As a preferred embodiment of the present invention, a funnel-type guiding structure in which the distance between the filaments and the guide shaft is gradually reduced is also proposed to facilitate the convergence of ions and the scattering of airflow.
在本发明的实施例中,每层细丝电极的方向相对于上一层细丝电极的方向,绕导引轴旋转的角度可由多种变化,例如为 2 π /N ,其中 N= 4 , 5 , 6 , 7 , 8 , 9 , 10 , 11 或 12 。由此,可构造四极场、六极场、八极场等。在一些实施例中,每层细丝电极的形状可为三角形、五边形等多边形。In an embodiment of the present invention, the direction of the rotation of each layer of the filament electrode relative to the direction of the upper layer of the filament electrode can be varied by a plurality of angles, for example, 2 π /N, where N = 4, 5 , 6 , 7 , 8 , 9 , 10 , 11 or 12 . Thereby, a quadrupole field, a hexapole field, an octapole field, or the like can be constructed. In some embodiments, the shape of each layer of filament electrodes may be a polygon such as a triangle, a pentagon, or the like.
在本发明的实施例中,构造使离子向所述导引轴会聚的电场的方式有许多种。例如,向相邻层细丝电极提供相位不同的高频电压,如互为反相的高频电压,以高频相位差为弧度2 π /M(M 为大于 1 的自然数 ) 逐渐变化的高频电压等。高频电压的幅值也可变化。又如,向各层细丝电极提供直流电压,在离子导引通道内的产生沿导引轴变化的直流电场强度,其分量包含使离子向导引轴会聚的电场。In an embodiment of the invention, there are many ways to construct an electric field that converges ions toward the guide axis. For example, a high-frequency voltage having a different phase is supplied to an adjacent layer filament electrode, such as a high-frequency voltage that is opposite to each other, and the high-frequency phase difference is an arc 2 π /M (M is a natural number greater than 1) Gradually changing high frequency voltage, etc. The amplitude of the high frequency voltage can also vary. As another example, a DC voltage is applied to each of the filament electrodes to produce a DC electric field strength that varies along the guide axis within the ion guide channel, the component of which includes an electric field that converges the ions toward the guide axis.
在本发明的实施例中,高频电压源包括多个高频高压开关,以产生矩形波高频电压。In an embodiment of the invention, the high frequency voltage source includes a plurality of high frequency high voltage switches to generate a rectangular wave high frequency voltage.
在本发明的实施例中,还可以让至少一部分层细丝电极上叠加不同的直流电位,以形成沿导引轴方向的电位梯度。In an embodiment of the invention, it is also possible to superimpose different direct current potentials on at least a portion of the layer filament electrodes to form a potential gradient in the direction of the guiding axis.
在本发明的实施例中,导引轴并不限定为直线,而是可为曲线形导引轴。在该实施例或其他实施例中,可进一步包括直流电压提供装置,使至少其中一部分层细丝电极的细丝之间叠加一个直流电压,以帮助离子沿着导引轴偏转。In an embodiment of the invention, the guide shaft is not limited to a straight line, but may be a curved guide shaft. In this or other embodiments, the DC voltage supply means may be further included to superimpose a DC voltage between the filaments of at least a portion of the layer of the filament electrodes to assist in deflecting the ions along the guide axis.
在本发明的实施例中,离子导引装置的至少一部分存在流动的气体,且导引轴方向的电位梯度所引起的离子迁移运动方向与轴向气流方向相反,使仅有特定离子迁移率的一部分离子得到有效传输。In an embodiment of the invention, at least a portion of the ion guiding device has a flowing gas, and the direction of the ion migration caused by the potential gradient in the direction of the guiding axis is opposite to the direction of the axial gas flow, so that only specific ion mobility is achieved. A portion of the ions are efficiently transported.
在本发明的一实施例中,至少一部分层细丝电极中细丝的间距设置以及高频电压设置使得进入离子导引装置的离子在此部分细丝所在空间的附近实现具有质量选择性的通过,阻挡或消灭。In an embodiment of the invention, the spacing of the filaments in at least a portion of the layer of filament electrodes and the setting of the high frequency voltage allow ions entering the ion guiding device to achieve mass-selective passage in the vicinity of the space in which the filaments are located. , block or destroy.
在本发明的另一实施例中,高频电压的设置以及导引轴方向的电位梯度设置使得进入离子导引装置的离子与中性气体分子发生有效碰撞,并使碰撞反应后生成的产物离子、碎片离子、或去溶剂化的离子得到有效地传输。In another embodiment of the present invention, the setting of the high frequency voltage and the potential gradient setting in the direction of the guiding axis cause the ions entering the ion guiding device to collide with the neutral gas molecules and cause the product ions generated after the collision reaction. , fragment ions, or desolvated ions are efficiently transported.
在本发明的实施例中,离子导引装置的至少一部分存在流动的气体,所述流动气体的气压范围在 10 至 10000 帕斯卡之间。在气流环境中,细丝的直径小于 0.5mm 以减小对气流的影响。作为一种实施方案,为了使细丝有效的固定,又不让固定装置干扰气流,将各层细丝固定在细丝形成的笼状导引通道外围的方案,即在外围设置固定支架或固定边框,将细丝缠绕、焊接或夹紧在固定支架或固定边框上。在使用较封闭的固定边框的实施例中,可在边框外壁设置排气孔以减少对气流的阻碍。In an embodiment of the invention, at least a portion of the ion guiding device has a flowing gas, the flowing gas having a gas pressure ranging from 10 to Between 10,000 Pascals. In airflow environments, the diameter of the filament is less than 0.5mm To reduce the impact on the airflow. As an embodiment, in order to effectively fix the filament without allowing the fixing device to interfere with the airflow, the layers of the filament are fixed on the periphery of the cage guiding channel formed by the filament, that is, the fixing bracket or the fixing is provided at the periphery. A frame that wraps, welds, or clamps a filament onto a mounting bracket or a fixed frame. In embodiments where a relatively closed fixed bezel is used, venting holes may be provided in the outer wall of the bezel to reduce obstruction to airflow.
本发明的实施例还提出一种离子导引装置组合结构,包括多个前述的离子导引装置的组合,其中至少部分离子导引装置在一第一方向上并联以实现导引轴的汇聚和 / 或发散。Embodiments of the present invention also provide an ion guiding device assembly comprising a combination of a plurality of the foregoing ion guiding devices, wherein at least a portion of the ion guiding devices are connected in parallel in a first direction to effect convergence of the guiding axes and / or divergent.
进一步地,在一些实施例中,至少部分离子导引装置在一第二方向上串联以实现导引轴的衔接。Further, in some embodiments, at least a portion of the ion guiding devices are connected in series in a second direction to effect engagement of the guiding shaft.
附图说明DRAWINGS
为让本发明的上述目的、特征和优点能更明显易懂,以下结合附图对本发明的具体实施方式作详细说明,其中:The above described objects, features, and advantages of the present invention will become more apparent from the aspects of the invention.
图1示出根据本发明实施例的直丝型离子导引器原理性示意图。1 shows a schematic diagram of a straight wire type ion guide according to an embodiment of the present invention.
图2示出本发明一实施例的直丝型离子导引器结构。Fig. 2 shows a structure of a straight wire type ion guide according to an embodiment of the present invention.
图3示出本发明一实施例的离子导引器形成的高频电场分布图。其中图3(a)是在通过导引轴的剖面上等位线分布,图3(b)是在垂直于导引轴的剖面上等位线分布。Fig. 3 is a view showing a high-frequency electric field distribution diagram formed by an ion guide according to an embodiment of the present invention. 3(a) is an equipotential line distribution on a section passing through the guide axis, and FIG. 3(b) is an equipotential line distribution on a section perpendicular to the guide axis.
图4示出本发明一实施例的离子导引器形成的轴向电位分布图。Fig. 4 is a view showing an axial potential distribution formed by an ion guide according to an embodiment of the present invention.
图5示出本发明一实施例的离子运动轨迹的仿真。Figure 5 shows a simulation of an ion motion trajectory in accordance with an embodiment of the present invention.
图6示出细丝电极用圆筒形支架固定的实例。Fig. 6 shows an example in which the filament electrode is fixed by a cylindrical stent.
图7示出细丝电极用立柱形支架固定的实例。Fig. 7 shows an example in which the filament electrode is fixed by a cylindrical bracket.
图8示出一个产生径向6极场分量的实施例。Figure 8 shows an embodiment that produces a radial 6-pole field component.
图9示出一个产生径向8极场分量的实施例。Figure 9 shows an embodiment that produces a radial 8-pole field component.
图10示出一个产生旋转多极场的实施例。Figure 10 illustrates an embodiment that produces a rotating multipole field.
图11示出用弹片将细丝绷紧的固定方式。Figure 11 shows the manner in which the filaments are tightened by means of elastic pieces.
图12示出用弹片将细丝焊牢并绷紧的固定方式。Figure 12 shows the manner in which the filaments are welded and taut by a spring.
图13示出本发明一实施例的弧线形导引轴的细丝离子导引装置。Figure 13 is a view showing a filament ion guiding device for an arcuate guide shaft according to an embodiment of the present invention.
图14示出本发明一实施例的混合正负离子流及引入碰撞气体反应的细丝离子导引装置。Figure 14 shows a filament ion guiding device for mixing positive and negative ion currents and introducing a collision gas reaction according to an embodiment of the present invention.
图15示出本发明一实施例的用空间周期性直流电位形成聚焦能力的离子导引装置,其中四层为一周期。Figure 15 is a diagram showing an ion guiding device for forming a focusing ability using a spatial periodic direct current potential according to an embodiment of the present invention, wherein four layers are one cycle.
图16示出本发明一实施例的用空间周期性直流电位形成聚焦能力的离子导引装置,其中六层为一周期。Figure 16 is a diagram showing an ion guiding device for forming a focusing ability using a spatial periodic direct current potential according to an embodiment of the present invention, wherein six layers are one cycle.
本发明的实施方式Embodiments of the invention
在强气流下,用交变电场会聚和导引带电粒子通常会遇到符合所需电场的电极结构,与在该电极结构影响下的气流对带电粒子运动的干扰之间的矛盾。避免这一矛盾的方法是采用对气流影响很小的细丝来做电极,然而很细的丝很难在空间摆布成所需的形状。Under a strong airflow, the use of an alternating electric field to converge and direct the charged particles typically encounters a contradiction between the electrode structure that conforms to the desired electric field and the interference of the airflow under the influence of the electrode structure on the motion of the charged particles. The way to avoid this contradiction is to use filaments that have little effect on the airflow to make the electrodes, but very thin filaments are difficult to place in the desired shape in space.
为此,本发明的实施例提出的离子导引器使用多层拉直的细丝交织,围成一种类似上海世博会的'东方之冠'建筑的空间结构。这种结构具有良好的通气性,不阻挡气流。在结构中央,形成一个笼状通道,并且在结构的外围,将构成通道的'丝'绷紧固定起来,以解决丝的位置稳定性和丝之间的绝缘问题。在每两层细丝之间,'丝'的轴向基本上为正交,因此其间电容可显著降低。To this end, the ion guide proposed by the embodiment of the present invention uses a plurality of layers of straightened filaments to form a space structure similar to the 'Oriental Crown' building of the Shanghai World Expo. This structure has good air permeability and does not block the air flow. In the center of the structure, a cage channel is formed, and at the periphery of the structure, the 'wire' constituting the channel is tightly fixed to solve the positional stability of the wire and the insulation problem between the wires. Between each two layers of filaments, the axial direction of the 'filaments' is substantially orthogonal, so the capacitance therebetween can be significantly reduced.
现在以图 1 的原理性示意图为例,说明这种直丝离子导引器的结构。可以理解,下面参照图 1 描述的离子导引器仅是为了说明目的,这些描述不应作为对本发明的离子导引器结构的限制。The structure of the straight wire ion guide will now be described by taking the schematic diagram of Fig. 1 as an example. It can be understood that reference is made to Figure 1 below. The ion guides described are for illustrative purposes only and should not be construed as limiting the structure of the ion guide of the present invention.
沿着虚拟的导引轴 z ,细丝电极共有 16 层,各层之间的形状大致上是相同的。每一层都含有一对与一导引轴 z 等距离的、相互平行的拉直的细丝 n.1 , n.2 (n 代表层数,本例中为 1 至 16) 。第二层的细丝 2.1 , 2.2 方向与第一层细丝 1.1 , 1.2 的方向垂直。也可以说是,第二层的细丝相对第一层细丝绕导引轴旋转了 90 度。各层细丝构成一个沿着导引轴 z 的笼状导引通道 21 。所有细丝绷直并固定在支架 16 上。所有的偶数层细丝 ( 即 n.1, n.2 中 n 为偶数的细丝 ) 通过电容 17 连接到高频电源 20 输出的一相 Y ,所有的奇数层细丝 ( 即 n.1, n.2 中 n 为奇数的细丝 ) 通过电容连接到高频电源的另一相 X (图中省略), X , Y 两相电压相位相反。支架 16 可以用印刷电路板制成,也可以用其他材料作出框架,再附上印刷电路板。细丝电极可以穿过印刷电路板上的小孔,焊接在印刷电路板的焊盘上。Along the virtual guide axis z, the filament electrode has 16 The layers, the shapes between the layers are substantially the same. Each layer contains a pair of straightened filaments n.1, n.2 that are equidistant from a guide axis z (n represents the number of layers, in this case 1 to 16) . The second layer of filaments 2.1, 2.2 is perpendicular to the direction of the first layer of filaments 1.1, 1.2. It can also be said that the filament of the second layer is rotated about the guiding axis with respect to the first layer of filaments. Degree. The layers of filaments form a cage guide channel 21 along the guide axis z. All filaments are stretched and secured to the bracket 16. All even layer filaments (ie n.1, n.2 n The even-numbered filaments are connected to the phase Y of the output of the high-frequency power source 20 through the capacitor 17, and all the odd-numbered filaments (i.e., n in the n.1, n.2 are odd-numbered filaments) The other phase X (omitted from the figure) connected to the high-frequency power supply by a capacitor, the X and Y phases are opposite in phase. Bracket 16 It can be made of printed circuit boards, or it can be framed with other materials and attached to printed circuit boards. The filament electrodes can be soldered to the pads of the printed circuit board through small holes in the printed circuit board.
如图 1 所示,各层细丝电极基本上使用大致上相同的结构,即两根平行的细丝。但是,本发明的替换实施例允许各层细丝电极的结构仅仅是相似,例如本例中,各层中两根细丝的间距可以变化。Figure 1 As shown, each layer of filament electrodes essentially uses substantially the same structure, i.e., two parallel filaments. However, alternative embodiments of the present invention allow the structure of the various layers of filament electrodes to be merely similar, such as in this example, the spacing of the two filaments in each layer can vary.
从图 1 可见,因为采用了细丝电极,且相邻层间的细丝方向不平行而是旋转了一个角度,因此大大地降低了层间电容,有利于减少高频电源的功耗。同时考虑到可能存在的射频放电及低真空中气体分子的扩散效应,细丝距导引轴的距离通常需不小于 1mm 。From Figure 1 It can be seen that since the filament electrode is used, and the filaments between adjacent layers are not parallel but rotated by an angle, the interlayer capacitance is greatly reduced, which is advantageous for reducing the power consumption of the high-frequency power source. Considering the possible RF discharge and the diffusion effect of gas molecules in low vacuum, the distance between the filament and the guiding axis is usually not less than 1mm.
本实施例的离子导引装置特别适用于装置的至少一部分或者周围存在流动的气体的环境中。流动气体的气压范围在典型地 10 至 10000 帕斯卡之间。The ion guiding device of the present embodiment is particularly suitable for use in an environment where at least a portion of the device or a surrounding gas is present. The pressure range of the flowing gas is typically 10 to 10,000 Between Pascals.
在一个实施例中,为减少导引器结构对气流的影响,细丝的直径小于 0.5mm 。In one embodiment, to reduce the effect of the introducer structure on the airflow, the filaments have a diameter of less than 0.5 mm.
可以作为细丝电极的材料典型地为金属,例如铜丝、镍丝、不锈钢丝等。为了提高电极的导电性,可以在细丝的表面镀金。The material which can be used as the filament electrode is typically a metal such as a copper wire, a nickel wire, a stainless steel wire or the like. In order to improve the conductivity of the electrode, gold may be plated on the surface of the filament.
为了在导引通道 21 内形成轴向电场,可以通过多个分压电阻 18 在各层细丝电极上加上直流电位。每层细丝电极之间连接一个分压电阻 18 。直流电压源 19 和分压电阻 18 一起,在导引通道 21 内形成直流的轴向电位梯度,以利于离子沿轴向传输。In order to form an axial electric field in the guiding channel 21, a plurality of voltage dividing resistors 18 may be passed. A direct current potential is applied to each of the filament electrodes. A voltage dividing resistor 18 is connected between each of the filament electrodes. The DC voltage source 19 and the voltage dividing resistor 18 are together in the guiding channel 21 An axial potential gradient of DC is formed to facilitate the transport of ions in the axial direction.
虽然在图 1 的设计中,各层细丝到导引轴 z 的距离都相等,但这个距离是可以根据需要来改变的。图 2 给出一种细丝离导引轴距离逐渐缩小的变化结构,这种结构具有较大的入口,有利于接受较为分散的入射离子,而随着离子向前传输,又能获得越来越强的会聚作用,起到了一个漏斗的作用。Although in the design of Figure 1, the filaments of each layer are equally spaced from the guide axis z, this distance can be varied as needed. figure 2 A variation structure in which the distance between the filament and the guiding axis is gradually reduced is given. This structure has a large inlet, which is favorable for accepting more dispersed incident ions, and can be obtained more and more as the ions are transmitted forward. The convergence of the role played a funnel role.
图 3 给出了图 2 所示离子导引装置内部电场分布。图 3(a) 是在第一层与第二层之间的平面上的等电位线分布。从图中可以看出,导引通道内的电场分布大致为一个四极场。这与以往的'离子漏斗'中的电场有本质上的不同。高频四极场在整个场区对离子都具有会聚作用。而'离子漏斗'中的旋转对称高阶场只有在离子靠近漏斗壁时才起到一个'反弹作用'。Figure 3 shows the internal electric field distribution of the ion guiding device shown in Figure 2. Figure 3 (a) Is the equipotential line distribution on the plane between the first layer and the second layer. As can be seen from the figure, the electric field distribution in the guiding channel is roughly a quadrupole field. This is essentially different from the electric field in the previous 'ion funnel'. The high frequency quadrupole field has a converging effect on ions throughout the field. The rotationally symmetric high-order field in the 'ion funnel' only plays a 'rebound effect' when the ions are close to the funnel wall.
同时这个斗形离子导引装置内的电场分布与传统的四极杆形成的电场也有所不同,如图 3(b) 所示的纵向剖面等位线可见,在导引轴附近,径向电位分布与四极杆形成的电位分布差别不大,但在细丝附近(电位线 31 呈同心圆)电位梯度陡然上升,离子在这些地方将受到很大的反弹力,防止它们逃出笼状导引通道。At the same time, the electric field distribution in the bucket ion guiding device is different from the electric field formed by the conventional quadrupole, as shown in Fig. 3(b). The longitudinal profile of the longitudinal profile is visible. In the vicinity of the guide axis, the radial potential distribution is not much different from the potential distribution formed by the quadrupole, but near the filament (potential line 31). Concentric circles) The potential gradient rises abruptly, and ions will be subjected to a large amount of repulsive force in these places, preventing them from escaping from the cage guiding channel.
图 4 显示了当采用分压电阻均匀分配直流电源电压时沿导引轴的直流分量电位线分布。这个电位梯度能帮助离子沿导引轴方向运动,避免离子在通道内长期滞留。直到从引出口 40 中引出,进入下一个低气压环境。Figure 4 It shows the potential component line distribution of the DC component along the guiding axis when the DC voltage is evenly distributed by the voltage dividing resistor. This potential gradient helps the ions move in the direction of the guiding axis, avoiding long-term retention of ions in the channel. Until the exit 40 Take out and enter the next low pressure environment.
图 5 是由电脑仿真获得的离子运动轨迹图。在仿真中,细丝上的高频电压分别为± 150V ( 0- 峰值),频率为 1MHz ,气压为 20torr ( 2660Pa )。细丝与导引轴间距在入口处为 5.25mm ,并逐步减少到 1.25mm ,细丝直径为 0.2mm ,两层细丝之间间距 1mm ,仿真结果显示质量数为 100 至上万的单价离子,绝大多数可以通过导引装置进入出口小孔 51 。Figure 5 is a plot of the ion motion trajectory obtained by computer simulation. In the simulation, the high frequency voltage on the filament is ± 150V ( 0- Peak), frequency is 1MHz, and air pressure is 20torr (2660Pa). The distance between the filament and the guide shaft is 5.25mm at the inlet and is gradually reduced to 1.25mm. The diameter of the filament is 0.2mm, the distance between the two layers of filaments is 1mm. The simulation results show that the mass number is 100 to tens of thousands of monovalent ions, and most of them can enter the outlet orifice 51 through the guiding device.
在以上的仿真试验中,细丝电极上加的高频电压为一个正弦波的射频电压。其实,高频电压源也可以采用多个高频高压开关,这时在细丝电极上产生的高频电压信号为一个矩形波高频电压。In the above simulation test, the high frequency voltage applied to the filament electrode is a sinusoidal RF voltage. In fact, the high-frequency voltage source can also use a plurality of high-frequency high-voltage switches, and the high-frequency voltage signal generated on the filament electrode is a rectangular wave high-frequency voltage.
在本发明的实施例中,用以固定细丝的支架,不仅可以做成图1所示的矩形,也可以是圆筒形。如图 6 所示,采用诸如陶瓷等硬质绝缘材料的筒壁 61 上可以事先做好印刷线路 63 和穿孔 64 ,细丝可以嵌焊在筒壁 61 上,筒壁上还开有许多排气孔 62 ,便于中性气体排出。In the embodiment of the present invention, the holder for fixing the filaments may be formed not only in a rectangular shape as shown in Fig. 1, but also in a cylindrical shape. Figure 6 As shown, a printed circuit 63 and a perforation 64 can be formed in advance on the wall 61 of a hard insulating material such as ceramic. The filament can be embedded on the wall 61, and a plurality of vent holes are formed in the wall. It is convenient for neutral gas to be discharged.
除了图 1 、 6 所示的框架形支架外,也可以采用图 7 所示的立柱形支架。立柱 71 , 72 , 73 , 74 可固定在锥孔板 75 上,而细丝 1 , 2 , 3 …则绕在立柱上一对立柱 71 , 73 和 72 , 74 上。这种结构的细丝走线位置不是靠孔来限定,而是由立柱不同高度处的直径来确定。In addition to the frame-shaped brackets shown in Figures 1 and 6, the column-shaped brackets shown in Figure 7 can also be used. Columns 71, 72, 73, 74 can be fixed on the cone plate 75, while the filaments 1 , 2 , 3 ... are wound around the column with a pair of columns 71 , 73 and 72 , 74 On. The position of the filaments of this structure is not defined by the holes, but by the diameter at different heights of the columns.
在本发明的实施例中,用细丝制作的离子导引装置不仅可以制成以产生四极场为主的会聚高频场的形式,也可以制成以 6 极、 8 极场等其他多极场为主的形式。如图 8 所示,可以将每层的细丝紧拉成一个三角形,三角形的中心位于导引轴上。下一层三角形细丝的方向相对于上一层的方向旋转 60 度。同样所有的偶数层细丝通过电容连接到高频电源的一相,所有的奇数层细丝通过电容连接到高频电源的另一相,两相电压相位相反。这样沿轴看过去细丝构成大卫 6 芒星的形状。离子导引通道内的电场除细丝附近以外,将以 6 极场为主。In the embodiment of the present invention, the ion guiding device made of the filament can be formed not only in the form of a concentrated high-frequency field mainly for generating a quadrupole field, but also in the form of 6 poles, 8 poles and other multi-pole field-based forms. Figure 8 As shown, the filaments of each layer can be pulled into a triangle with the center of the triangle on the guide shaft. The direction of the next layer of triangular filaments is rotated relative to the direction of the upper layer. Degree. Similarly, all of the even-numbered filaments are connected by capacitance to one phase of the high-frequency power supply, and all of the odd-numbered filaments are connected by capacitance to the other phase of the high-frequency power supply, and the two-phase voltages are opposite in phase. This way, the filaments are seen along the axis to form David 6 The shape of the star. The electric field in the ion guiding channel will be dominated by the 6-pole field except for the vicinity of the filament.
又如图 9 所示,如果每层都有四根细丝(如 911 , 912 , 913 , 914 …)拉成正方形形状(在四角处横竖边相互接触),下一层的正方形(由丝 921 , 922 , 923 , 924 构成)相对于上一层绕导引轴旋转 45 度角,这样就形成以产生 8 极场为主的离子导引装置。 6 、 8 极场和 4 极场相比,在中心部分的会聚作用较弱,但在外围会聚作用较强。依照本发明实施例构建的离子导引器的一个优点体现在可以合理的选用、调配中心或外围的会聚性能,并与细丝附近的离子反弹性能相结合,以适应不同特性的离子源和气流特性下的导引要求。As shown in Figure 9, if there are four filaments on each layer (such as 911, 912, 913, 914) ...) drawn into a square shape (contacting each other at the four corners), the square of the next layer (consisting of wires 921, 922, 923, 924) is rotated relative to the upper layer about the guide axis 45 The angle of the angle is such that an ion guiding device that produces an 8-pole field is formed. 6, 8 poles and 4 Compared with the polar field, the convergence in the central part is weak, but the convergence at the periphery is stronger. One advantage of the ion guide constructed in accordance with embodiments of the present invention is that it can be rationally selected, blended at the center or periphery for convergence, and combined with ion rebound performance near the filament to accommodate different characteristics of the ion source and gas flow. Guidance requirements under characteristics.
除了上述角度之外,旋转角度还可为 弧度2 π /N , N= 5 , 7 , 9 , 10 , 11 或 12 。In addition to the above angles, the angle of rotation can be radians 2 π /N , N = 5 , 7 , 9 , 10 , 11 or 12 .
虽然在以上描述的实施例中,每层细丝之间绕导引轴旋转的角度保持恒定,例如 90 °, 60 °, 45 °等,但是在其他实施例中,每层细丝之间绕导引轴旋转的角度并不一定是固定的。例如图 10 所示的离子导引器方案里,从第二层细丝起,每层较上一层旋转的角度分别为: 90 , 105 , 90 , 105…... 度;即层( 12.1 , 12.2 )较层( 11.1 , 11.2 )转 90 度,层( 13.1 , 13.2 )较层( 12.1 , 12.2 )转 105 度。在此,如果还是将所有的偶数层细丝通过电容连接到高频电源的一相,所有的奇数层细丝通过电容连接到高频电源的另一相,且这两相的电压相位相反,那么,这些细丝会形成一个沿着导引轴逐步旋转的四极场导引通道。这种离子导引器在传输离子过程中,离子云形状也会发生旋转,使传输通道在各向更为均等,也可能更加适合存在回转气流的情况。Although in the embodiments described above, the angle of rotation between the guide filaments of each layer remains constant, such as 90 °, 60 °, 45 °, etc., but in other embodiments, the angle of rotation of each layer of filaments about the guide axis is not necessarily fixed. For example, in the ion guide scheme shown in Figure 10, the angle of rotation of each layer from the second layer of filaments is: 90, 105, 90, 105... degrees; that is, the layer (12.12, 12.2) turns 90 degrees to the layer (11.11, 11.2), and the layer (13.1, 13.2) Level (12.12, 12.2) to 105 Degree. Here, if all of the even-numbered filaments are still connected to one phase of the high-frequency power source through a capacitor, all of the odd-numbered filaments are connected to another phase of the high-frequency power source through a capacitor, and the voltages of the two phases are opposite in phase. Then, the filaments form a quadrupole field guiding channel that rotates stepwise along the guiding axis. In the ion guide, the shape of the ion cloud also rotates during the ion transport, making the transmission channel more uniform in all directions, and may be more suitable for the presence of the swirling airflow.
作为更为奇异的实施例,各层细丝之间的高频电压的相位差可以不是 180 度。如果层间的高频电压的相位相差 120 度(或 90 度),这样每隔 3 层(或四层),高频电压的相位绕过了 1 周。这一实施例可推广到令邻近相邻层的高频相位差为弧度 2 π /M ,顺序提供同频 M 相高频电压给 1 到 M 层细丝电极,并使 M 层以后继续这个相位序列,其中 M 为大于 1 的自然数。利用层间周期性的多相高频电场,可以产生轴向行波,以利于离子向导引方向传输。有利的是,在这种情况下,就不必要施加轴向直流电位梯度来推动离子。As a more singular embodiment, the phase difference of the high frequency voltage between the filaments of each layer may not be 180 degrees. If the phase of the high frequency voltage between the layers is different 120 degrees (or 90 degrees), so that every 3 layers (or 4 layers), the phase of the high-frequency voltage is bypassed for 1 week. This embodiment can be extended to make the high frequency phase difference of adjacent adjacent layers to be arc 2 π /M , sequentially providing the same frequency M phase high frequency voltage to the 1 to M layer filament electrode, and the M layer continues this phase sequence later, where M is greater than 1 Natural number. By using the periodic multi-phase high-frequency electric field between the layers, an axial traveling wave can be generated to facilitate the ion transmission in the guiding direction. Advantageously, in this case it is not necessary to apply an axial direct current potential gradient to push the ions.
以上给出了高频电压的相位沿着各细丝电极层呈周期性变化的例子。在其他实施例中,可向相邻层细丝电极提供仅仅是相位不同的高频电压来构造电场,这一电场包含使离子向导引轴会聚的分量。The example in which the phase of the high-frequency voltage periodically changes along the respective filament electrode layers is given above. In other embodiments, an electric field can be constructed by providing only high frequency voltages of different phase to the adjacent layer filament electrodes, the electric field comprising a component that converges the ions toward the guiding axis.
当然,当存在与离子导引方向一致的强定向气流的情况下,即使没有轴向直流电位梯度的帮助(沿导引轴方向的电位梯度为负时,对正离子起正向帮助)仅依靠高频电场一定的会聚作用离子也能得到有效地传输。当该定向气流的速度足够大时,可以让导引轴方向的电位梯度阻止离子的正向传输,这时电场引起离子迁移运动的方向与轴向气流方向相反,如果离子迁移率较大,则不能被有效地传输,而迁移率较小的一部分离子得到有效的传输。Of course, when there is a strong directional airflow in the same direction as the ion guiding direction, even if there is no help of the axial DC potential gradient (the potential gradient in the direction of the guiding axis is negative, the positive ion is positively assisted) A certain concentration of ions of the high-frequency electric field can also be efficiently transmitted. When the velocity of the directional airflow is sufficiently large, the potential gradient in the direction of the guiding axis can prevent the forward transmission of ions, and the direction of the ion migration motion caused by the electric field is opposite to the axial airflow direction. If the ion mobility is large, It cannot be transmitted efficiently, and a part of ions with a small mobility is efficiently transmitted.
从安装工艺来看,应力图使各条细丝拉直绷紧。导引通道外部的细丝安装支架应当加工得牢固且准确。为了使细丝绷紧,图 11 给出立柱式设计中采用弹性较好的钢片卡簧 111 来提供张力,并用槽 112 限制细丝 1 ,来固定其轴向位置的方法。对于框架式支架和用印刷电路板来安装细丝的设计,图 12 给出用弹性焊片绷紧细丝的方案。图中,细丝 1 , 3 等穿过印刷电路板上的小孔 122 ,焊接在弹性焊片 120 上的焊孔 121 中,而弹性焊片则焊在印刷电路板的导电电路 123 上。同时示出的还有焊在同一块印刷电路板上的部分阻容器件 124 ,表示该电路板可以同时用以安装这些器件以及引线、连接器等等,方便地实现高频电压耦合、直流分压等功能。From the perspective of the installation process, the stress map straightens and tightens the individual filaments. The filament mounting bracket outside the guiding channel should be processed firmly and accurately. In order to tighten the filament, Figure 11 The steel column retainer 111 with better elasticity is used in the column design to provide tension, and the slot 112 is used to limit the filament 1 , to fix its axial position. For framed brackets and designs that use a printed circuit board to mount the filaments, Figure 12 shows a solution for tightening the filaments with elastic tabs. In the picture, filaments 1 , 3 Waiting through the small holes 122 on the printed circuit board, soldering into the soldering holes 121 on the elastic soldering piece 120, and the elastic soldering pieces are soldered to the conductive circuits of the printed circuit board 123 On. Also shown is a partial refractory member 124 soldered to the same printed circuit board. It means that the circuit board can be used to install these devices as well as leads, connectors, etc., and it is convenient to implement functions such as high-frequency voltage coupling and DC voltage division.
在本发明的较佳实施例中,各层细丝电极所在平面与导引轴基本上垂直。例如,各层细丝电极所在平面与导引轴的夹角设置在 85 °至 95 ° 之间。当然,细丝的走向与导引轴不完全垂直也不会对离子的汇聚能力产生严重影响。典型地,可以定义细丝所在平面与导引轴的夹角范围是 90+/-20 度,即 70 ° -110 ° 。而本发明的实施例所定义的导引轴并不一定是直线,它可以包含一段曲线。图 13 展示 了这种弧线形直丝电极离子导引装置。图中导引轴 132 为一条圆弧,离子和中性气体流 131 沿导引轴入口一端的切线方向进入导引通道。离子受到汇聚电场的作用聚集到导引轴附近,并顺着导引轴的弧线被引向出口 133 。而中性气体流则沿着原来方向冲向排气口 135 。除了和直导引管一样的叠加轴向电位梯度以外,本例中,每个奇数层的两根竖直细丝,如细丝 134.1 , 134.2 之间还可以再叠加一个直流电位差,以使得离子进一步获得偏转力,防止离子被强气流冲出导引通道。In a preferred embodiment of the invention, the layers of the filament electrodes of each layer are substantially perpendicular to the guide axis. For example, the angle between the plane of each layer of filament electrodes and the guide axis is set at 85 ° to 95 ° Between. Of course, the orientation of the filaments is not completely perpendicular to the guiding axis and does not have a serious impact on the ability of the ions to converge. Typically, it can be defined that the angle between the plane of the filament and the guide axis is 90 +/- 20 degrees, ie 70 ° -110 °. However, the guide axis defined by the embodiment of the present invention is not necessarily a straight line, and it may include a curve. Figure 13 shows this curved wire electrode ion guide. Guide axis in the figure 132 For an arc, the ion and neutral gas stream 131 enters the guide channel in a tangential direction from one end of the inlet of the guide shaft. The ions are concentrated near the guiding axis by the concentrated electric field and are led to the exit along the arc of the guiding axis. . The neutral gas flow rushes toward the exhaust port 135 in the original direction. In addition to the superimposed axial potential gradients of the straight guide tubes, in this example, two vertical filaments of each odd layer, such as filament 134.1, A DC potential difference can be superimposed between 134.2 to further obtain the deflection force of the ions, preventing the ions from being flushed out of the guiding channel by the strong airflow.
以上各实施方案目的只是为了说明多层细丝离子导引装置的可行的构造方法,和一部分技术细节,以显示该导引装置的可实施性。然而,本发明并不局限于以上给出的几种走丝形式和电场结构。例如,每层细丝还可以搭成相似的五边形,五角星形或长方形,甚至六、七边及以上形状。 可以理解,在这些实施例中,较佳地仍是使各层细丝电极保持大致上相同的结构。但是允许各层细丝电极的多边形是有尺寸差别的相似,或者允许各层细丝电极的多边形之间出现略微变形。The above various embodiments are only intended to illustrate a possible construction method of the multilayer filament ion guiding device, and a part of the technical details to show the implementability of the guiding device. However, the invention is not limited to the several wire-forming forms and electric field structures given above. For example, each layer of filaments can also be formed into a similar pentagon, pentagram or rectangle, or even six or seven sides and above. It will be appreciated that in these embodiments, it is preferred that the layers of filament electrodes remain substantially identical. However, the polygons of the respective filament electrodes are allowed to have similarities in size difference, or slight deformation between the polygons of the respective filament electrodes is allowed.
并且, 附加在细丝上的各电压信号也可以是方波、锯齿波,脉冲序列,而且还可以是正弦波、方波与脉冲序列的组合。产生径向束缚电场的交流电压信号,并不一定要等幅值地分布在各层细丝上,而是可以同导引装置中 至少一部分层细丝电极中细丝的间距设置相结合来选择离子。以图 3a 中所描述的具有四极射频电场分布的导引装置为例,该四极电场对不同质荷比的离子轨迹的稳定性的影响可用 q 参数描述,其数值大致与细丝间距的平方及通过离子的质荷比成反比,与附加在细丝上的射频电压幅度成正比。 可以在具体设计中根据通过离子的质荷比、结合结构中细丝的间距,通过如图1中的阻容网络 17 与 18 的取值,来静态或 动态地改变射频电压,控制某一选定质荷比范围的离子具有对应稳定离子轨迹的q参数。从而实现对通过离子的质量选择下的通过或排除。同时,当细丝层间的射频电压幅度出现变化时,与上所述的径向选择类似,也可在导引装置的轴向产生等效势垒,该势垒也是随离子质荷比大小变化的,可以用来实现对某些离子的暂时阻截。利用这些特点与本装置也可作为离子去溶剂化器使用,实现随通过去溶剂化过程中离子质荷比动态变化的质荷比通过窗口,达到最好的离子传输效果。and, The voltage signals attached to the filaments may also be square waves, sawtooth waves, pulse trains, and may also be a combination of sine waves, square waves and pulse sequences. The alternating voltage signal generating the radially bound electric field does not have to be equally distributed on the layers of filaments, but can be in the same guiding device The spacing of the filaments in at least a portion of the layer of filament electrodes is combined to select ions. Figure 3a For example, the guidance device with a quadrupole RF electric field distribution is described. The influence of the quadrupole electric field on the stability of ion trajectories with different mass-to-charge ratios can be used. Parameter description, the value is roughly inversely proportional to the square of the filament spacing and the mass-to-charge ratio of the ions, and is proportional to the amplitude of the RF voltage attached to the filament. In the specific design, according to the mass-to-charge ratio of the ions, the spacing of the filaments in the bonding structure, through the values of the RC networks 17 and 18 in Fig. 1, static or The RF voltage is dynamically changed, and ions of a selected range of mass-to-charge ratios have q parameters corresponding to stable ion trajectories. Thereby achieving the passage or elimination of the quality of the passing ions. At the same time, when the amplitude of the RF voltage between the filament layers changes, similar to the radial selection described above, an equivalent barrier can also be generated in the axial direction of the guiding device, and the barrier is also in accordance with the ion mass-to-charge ratio. The change can be used to achieve temporary interception of certain ions. Using these features and the device can also be used as an ion desolvator to achieve the best ion transport effect through the window through the mass-to-charge ratio dynamic change of the ion mass-to-charge ratio during desolvation.
进一步,产生轴向电场的直流电位,也并不一定要等差地分布在各层细丝上。作为替代,可以根据需要通过更改电阻18网络取值来设定其分布,并根据需要来改变其分布。例如,可以在某几层上暂时加较负直流电压,使离子在这段时间在这几层的区域被捕获。然后,改变为正常的梯度分布,将捕获的离子释放。另一个例子是,利用轴向电场加速离子,甚至用交变的轴向或横向电场诱导离子在空间中高速振动的方法,增加离子与中性分子的碰撞几率及强度,以实现离子在高气压条件下与中性气体碰撞反应,并进而把反应产物离子、离子碎片或去溶剂化的产物有效地导引出来进行分析。Further, the direct current potential that generates the axial electric field does not have to be equally distributed on the respective layers of filaments. Alternatively, the distribution of the resistor 18 network can be set as needed to change its distribution and change its distribution as needed. For example, a relatively negative DC voltage can be temporarily applied to certain layers to allow ions to be trapped in the areas of these layers during this time. Then, change to a normal gradient distribution to release the trapped ions. Another example is the use of an axial electric field to accelerate ions, or even an alternating axial or transverse electric field to induce high-speed vibration of ions in space, increasing the collision probability and intensity of ions with neutral molecules to achieve ions at high pressure. Under the conditions, it collides with the neutral gas, and then the reaction product ions, ion fragments or desolvated products are effectively guided for analysis.
限于篇幅,在此并不一一例举组合上述各种变化的实施例,将上述的各种变化的一部分组合来构成实际可用的实例,是本领域普通技术人员的基本能力。Without limiting the scope, it is not an exemplification of the embodiments in which the various changes described above are combined, and a combination of the various variations described above to constitute a practically usable example is a basic ability of one of ordinary skill in the art.
例如本导引装置中的一部分或全部直丝电极可用电阻发热材料制成,通过在电阻丝两端间附加加热电流源装置,可以在本装置内附加加热功能,并辐射出红外线,以产生对导引装置内的目标离子的热辅助去溶剂化,热解离,红外辐射解离等效果。此外,作为电阻丝的一个变体,在本装置使用高频交流电源工作时,可用磁导率较高的材料制作直丝电极,利用类似电磁炉的磁感涡流加热金属丝来达到相同目的,此时可省去额外的加热电流源装置。For example, some or all of the straight wire electrodes in the guiding device can be made of a resistance heating material. By adding a heating current source device between the two ends of the electric resistance wire, a heating function can be added to the device, and infrared rays can be radiated to generate a pair. The heat-assisted desolvation, thermal dissociation, and infrared radiation dissociation of the target ions in the guiding device. In addition, as a variant of the resistance wire, when the device is operated with a high-frequency alternating current power source, a straight wire electrode can be made of a material having a high magnetic permeability, and the magnetic wire is heated by a magnetic induction eddy current like an induction cooker to achieve the same purpose. Additional heating current source devices can be eliminated.
又例如通过复用多个本导引装置结构 ( 如图 14 中 141.1 与 141.2) 共用一部分细丝(如图 14 中 143.1 与 143.2 )或形成的导引装置组合还可以进一步提升本装置的离子导通能力。如图 14 进一步所示,通过串联多个细丝离子导引结构,如图中 141 , 142 , 143 所示,可实现该阵列中多个虚拟导引轴轴的分散或汇聚、重合,使安置在离子导引结构上下游的多个离子源及下级离子分析装置间还可以实现一对多,多对一、多对多的离子源 - 分析器配合,即离子流分流器,复用器及交换器的作用。For example, by multiplexing a plurality of the guiding device structures (such as 141.1 and 141.2 in Fig. 14), a part of the filaments are shared (as shown in Fig. 14). 14 The combination of 143.1 and 143.2) or the formed guide device can further enhance the ion conduction capability of the device. As further shown in FIG. 14, a plurality of filament ion guiding structures are connected in series, as shown in the figure. 141, 142, 143 As shown, the dispersion or convergence and overlap of the plurality of virtual guide axes in the array can be realized, so that a plurality of ion sources and lower ion analysis devices disposed upstream and downstream of the ion guiding structure can realize one-to-many and more For one, many to many ion sources - Analyzer coordination, ie the role of ion current shunts, multiplexers and exchangers.
图 14 所示的导引装置组合也可以让不同极性的正离子流 144 、负离子流 145 以及中性分子流 146 等进行汇聚、混合及分离,以引发分子离子反应与电荷转移反应使目标离子碎裂,并获得分离的产物离子流,用于后级的串级质谱分析。例如在所示的系统中,通过外周电路系统可在导引系统的各层细丝间附加由左向右依次递减的直流电位偏置,使正离子流 144 受到沿流动方向逐级下降的导引轴向电位分布 147 的作用,同时使逆向的负离子流 145 收到沿流动方向逐级上升的导引轴向电位分布 148 的作用,流入导引结构中段 142 互相混合。正负离子流两者在串联导引结构中段 142 中由于内部交流四极场作用,向导引结构 142 的中轴汇聚,并发生反应,可得到所谓电荷转移解离( ETD )方法的离子碎裂效果。反应后得到的新正负离子流,可通过在导引结构中段的两侧细丝组 142.1 与 142.2 之间进一步叠加直流偏转电位,使其向各自的出口通道偏转而分离。更进一步,还可利用细丝离子导引结构的通透性,可向中段导引结构 142 中引入合适的碰撞气体 146 如氩气,异丁烷等以增加正离子流 144 与负离子流 145 的停留时间,并可通过碰撞气体 146 做催化剂增加电荷转移效率以增加解离效果。 The combination of guides shown in Figure 14 also allows positive ion currents 144, negative ion currents 145, and neutral molecular flows of different polarities. 146 The polymerization, mixing and separation are carried out to initiate molecular ion reaction and charge transfer reaction to fragment the target ions, and a separated product ion stream is obtained for subsequent cascade mass spectrometry. For example, in the system shown, the peripheral circuit system can add a DC potential offset that is successively decreasing from left to right between the layers of the guiding system to make the positive ion current 144 is subjected to a guided axial potential distribution 147 that decreases stepwise along the flow direction, while causing the reverse negative ion current 145 to receive a pilot axial potential distribution that rises stepwise along the flow direction. The effect of the inflow into the guiding structure middle section 142 is mixed with each other. Both the positive and negative ion currents in the mid-section of the series guiding structure 142 are directed toward the guiding structure 142 due to the internal alternating quadrupole field. The central axis converges and reacts to obtain the ion fragmentation effect of the so-called charge transfer dissociation (EDD) method. The new positive and negative ion currents obtained after the reaction can pass through the filament groups 142.1 on both sides of the guiding structure The DC deflection potential is further superimposed between 142.2 to deflect and separate to the respective exit channels. Furthermore, the permeability of the filament ion guiding structure can be utilized to guide the structure to the middle section 142 A suitable collision gas 146 such as argon, isobutane or the like is introduced to increase the residence time of the positive ion stream 144 and the negative ion stream 145, and can pass the collision gas 146. Catalysts increase the charge transfer efficiency to increase the dissociation effect.
最后还要指出,离子在通过本发明的离子导引器时所受到的会聚作用也可以通过在各细丝上仅仅施加特殊的直流电压得以实现。当各细丝电极上施加不同的直流电压时, 在离子导引通道内的产生沿导引轴变化的直流电场强度。配置这些直流电压,使得直流电场强度的分量包含使离子向导引轴会聚的电场。 现在以图 15 为例说明其工作原理。这里每一层都含有一对相互平行的拉直的细丝 n.1 , n.2 (n 代表层数,且 n 为自然数 ) 。第二层的细丝 2.1,2.2 方向与第一层细丝 1.1, 1,2 的方向垂直,第三层的细丝方向与第二层细丝的方向垂直,第三层的细丝方向与第一层细丝的方向平行,并以此类推。各层细丝上的电位见图中标出,其变化关系也用图线 U 表现出来。可以看出,每层细丝的电压除了一个逐步递减的直流量外,还要在各偶数层上相间地叠加 +/- Δ V 。比如,Δ V=10V 时,各层电位即为 130V , 110V(120-10) , 110V , 110V(100+10) , 90V , 70V(80-10) , 70V , 70V(60+10) , 50V , 30V(40-10) , 30V , 30V(20+10) , 10V 。由此产生的直流电场强度沿导引轴呈 4 层一组的周期性变化。这一特征接近于一串电位来回反转的直流四极透镜,会使离子沿导引轴向运动时产生周期性的聚焦和 散焦。离子在气流和直流电场梯度的共同作用下在离子导引器轴向可以达到几十至几百米每秒的速度,以这样的速度在以几毫米为一个重复聚焦、散焦单元的距离内运动,就等同于离子在同一位置经历一个几千至几十万赫兹交变电压所产生四极场的作用,从而达到离子沿径向方向的聚焦。又以图 16 为例,相邻三对(层)细丝上施加相等的直流电压,三层为一小组,组间电压递减,这时产生的直流电场也会使离子沿引导器轴向运动时产生周期性的( 6 层一周期)聚焦和散焦现象,聚焦散焦与离子碰撞冷却相结合,达到离子沿径向方向的会聚。Finally, it is pointed out that the convergence of the ions as they pass through the ion guide of the invention can also be achieved by applying only a special DC voltage across the filaments. When different DC voltages are applied to the respective filament electrodes, A DC electric field strength that varies along the guiding axis is generated within the ion guiding channel. These DC voltages are configured such that the component of the DC electric field strength includes an electric field that converges ions toward the steering axis. Now take Figure 15 Take an example to illustrate its working principle. Each layer here contains a pair of parallel straight filaments n.1, n.2 (n represents the number of layers, and n is a natural number). The second layer of filament 2.1, 2.2 Direction with the first layer of filaments 1.1, 1, 2 The direction is perpendicular, the filament direction of the third layer is perpendicular to the direction of the second layer of filaments, the filament direction of the third layer is parallel to the direction of the first layer of filaments, and so on. The potentials on the filaments of each layer are shown in the figure, and the relationship is also shown by the U Show it out. It can be seen that the voltage of each layer of filaments is superimposed with +/- ΔV on each even layer in addition to a gradually decreasing amount of direct current. For example, when Δ V=10V, the potential of each layer is 130V. , 110V (120-10), 110V, 110V (100+10), 90V, 70V (80-10), 70V, 70V (60+10), 50V, 30V (40-10), 30V, 30V (20+10), 10V. The resulting DC electric field strength is along the guiding axis. The periodic variation of a layer. This feature is close to a series of DC quadrupole lenses that reverse the potential and cause periodic focusing and focusing of ions as they move along the guiding axis. Defocused. The ion can reach a speed of several tens to several hundred meters per second in the axial direction of the ion guide under the action of the airflow and the direct current electric field gradient, at such a speed within a distance of a few millimeters as a refocusing and defocusing unit. Movement is equivalent to the action of a quadrupole field generated by an ion undergoing an alternating voltage of several thousand to several hundreds of thousands of hertz at the same position, thereby achieving focusing of the ions in the radial direction. Again 16 For example, an equal DC voltage is applied to three adjacent pairs of layers, and the three layers are a group. The voltage between the groups is decremented. The DC electric field generated at this time also causes the ions to move along the axial direction of the guide. Sexual ( 6 Layer-by-cycle) focusing and defocusing, focusing defocusing combined with ion collision cooling to achieve convergence of ions in the radial direction.
以上示例性的描述了本发明的较佳实施例和各种变化例,本领域普通技术人员可在以上的较佳实施例和变化例的基础上进行各种组合和替换,得到各种变化结构,但是这些变化结构都涵盖在本发明由权利要求书所定义的保护范围内。The above description of the preferred embodiments and various modifications of the present invention can be made by those skilled in the art in various combinations and substitutions on the basis of the above preferred embodiments and variations. However, such variations are intended to be included within the scope of the invention as defined by the appended claims.

Claims (34)

  1. 一种离子导引装置,包含:An ion guiding device comprising:
    沿着一定义离子导引方向的导引轴分布的多层细丝电极,每层细丝电极包含至少两根距所述导引轴一定距离的、拉直的细丝,每层细丝电极相对于相邻层细丝电极绕所述导引轴旋转一定的角度,使多层细丝电极围绕所述导引轴形成通透的笼状离子导引通道;以及a plurality of filament electrodes distributed along a guiding axis defining a direction of ion guiding, each layer of filament electrodes comprising at least two straight filaments at a distance from the guiding axis, each layer of filament electrodes Rotating a certain angle with respect to the adjacent layer filament electrode about the guiding axis, so that the multilayer filament electrode forms a transparent cage ion guiding channel around the guiding axis;
    电源装置,向各层细丝电极提供电压,以至少构造使离子向所述导引轴会聚的电场。A power supply device provides a voltage to each of the layers of filament electrodes to at least configure an electric field that converges ions toward the guide axis.
  2. 根据权利要求1的离子导引装置,其特征在于,还包括位于所述多层细丝电极形成的离子导引通道之外的悬拉支架,所述多层细丝电极的细丝固定于所述悬拉支架。The ion guiding device according to claim 1, further comprising a suspension holder located outside said ion guiding channel formed by said plurality of filament electrodes, said filament of said multilayer filament electrode being fixed to said Said suspension bracket.
  3. 根据权利要求1的离子导引装置,其特征在于,每层细丝电极所在的平面与所述导引轴的夹角介于70°至110°之间。The ion guiding device according to claim 1, wherein an angle between a plane in which each of the filament electrodes is located and the guiding shaft is between 70° and 110°.
  4. 根据权利要求1的离子导引装置,其特征在于,每层细丝电极所在的平面与所述导引轴的夹角范围为85°至95°。The ion guiding device according to claim 1, wherein an angle between a plane in which each of the filament electrodes is located and the guiding shaft ranges from 85 to 95.
  5. 根据权利要求1的离子导引装置,其特征在于,每层细丝电极的每根细丝与所述导引轴的距离相等。The ion guiding device according to claim 1, wherein each of the filaments of each of the filament electrodes has the same distance from the guide shaft.
  6. 根据权利要求5的离子导引装置,其特征在于,每层细丝电极中至少有两根细丝相互平行。The ion guiding device according to claim 5, wherein at least two of the filament electrodes of each layer are parallel to each other.
  7. 根据权利要求1的离子导引装置,其特征在于,每层细丝电极的方向相对于上一层细丝电极的方向,绕导引轴旋转的角度为2π/N,其中N= 4,5,6,7,8,9,10,11或12。The ion guiding device according to claim 1, wherein the direction of each of the filament electrodes is rotated by 2π/N around the guiding axis with respect to the direction of the upper layer of the filament electrodes, wherein N = 4,5,6,7,8,9,10,11 or 12.
  8. 根据权利要求1、3或4的离子导引装置,其特征在于,每层细丝电极包含一对细丝,且该对细丝与导引轴距离基本相等且相互基本平行。The ion guiding device according to claim 1, 3 or 4, wherein each of the filament electrodes comprises a pair of filaments, and the pair of filaments are substantially equal in distance from the guide axis and substantially parallel to each other.
  9. 根据权利要求8的离子导引装置,其特征在于,每层细丝电极的方向相对于上一层细丝电极的方向,绕导引轴旋转的角度为π/2。The ion guiding device according to claim 8, wherein the direction of each of the filament electrodes is rotated by an angle of π/2 around the guiding axis with respect to the direction of the upper layer of the filament electrodes.
  10. 根据权利要求1或9的离子导引装置,其特征在于,所述电源装置包含高频电压源,向各层细丝电极提供高频电压以至少构造使离子向所述导引轴会聚的电场。The ion guiding device according to claim 1 or 9, wherein said power supply device comprises a high-frequency voltage source for supplying a high-frequency voltage to each of the filament electrodes to at least configure an electric field for converging ions toward said guiding axis .
  11. 根据权利要求10的离子导引装置,其特征在于,所述高频电压源向各层细丝电极提供高频电压的方式包括,向相邻层细丝电极提供相位不同的高频电压。The ion guiding device according to claim 10, wherein said high frequency voltage source supplies a high frequency voltage to each of the plurality of filament electrodes, and comprises supplying a high frequency voltage of a different phase to the adjacent layer filament electrodes.
  12. 根据权利要求10的离子导引装置,其特征在于,所述高频电压源向各层细丝电极提供高频电压的方式包括,提供互为反相的高频电压给相邻层细丝电极。The ion guiding device according to claim 10, wherein said high frequency voltage source supplies a high frequency voltage to each of the plurality of filament electrodes, comprising: providing mutually inverted high frequency voltages to adjacent layer filament electrodes .
  13. 根据权利要求11或12的离子导引装置,其特征在于,各层细丝电极中至少加同相高频电压的一组细丝电极与导引轴的距离沿导引轴逐渐缩小。The ion guiding device according to claim 11 or 12, wherein a distance between the set of filament electrodes to which at least the in-phase high-frequency voltage is applied to the respective layers of the filament electrodes and the guide shaft is gradually reduced along the guiding axis.
  14. 根据权利要求10的离子导引装置,其特征在于,所述电源装置包含直流电压源,让至少一部分层细丝电极上叠加不同的直流电位,以形成沿所述导引轴方向的电位梯度。 The ion guiding apparatus according to claim 10, wherein said power supply means comprises a direct current voltage source such that at least a portion of the layer filament electrodes are superimposed with different direct current potentials to form a potential gradient in the direction of said guiding axis.
  15. 根据权利要求11的离子导引装置,其特征在于,所述高频电压源向各层细丝电极提供高频电压的方式包括,顺序提供同频M相高频电压给1到M层细丝电极,相邻层的高频相位差为2π/M,并使M层以后继续这个相位序列,M为大于1的自然数。 The ion guiding device according to claim 11, wherein said high frequency voltage source supplies a high frequency voltage to each layer of the filament electrodes, and comprises sequentially supplying the same frequency M phase high frequency voltage to the 1 to M layer filaments. The high frequency phase difference of the electrodes and adjacent layers is 2π/M, and the M layer continues this phase sequence later, and M is a natural number greater than 1.
  16. 根据权利要求10的离子导引装置,所述高频电压源向各层细丝电极提供高频电压的方式包括,向各层细丝电极提供不同的高频电压幅值。 The ion guiding device according to claim 10, wherein said high frequency voltage source supplies a high frequency voltage to each of the plurality of filament electrodes including providing different high frequency voltage amplitudes to the respective layer of filament electrodes.
  17. 根据权利要求1或2的离子导引装置,其特征在于,所述电源装置包括直流电压源,以向各层细丝电极提供直流电压,在所述离子导引通道内的产生沿导引轴变化的直流电场强度,其分量包含使离子向所述导引轴会聚的电场 The ion guiding device according to claim 1 or 2, wherein said power supply means comprises a direct current voltage source for supplying a direct current voltage to each layer of the filament electrodes, and generating in said ion guiding channel along the guiding axis a varying DC electric field strength whose component contains an electric field that converges ions toward the guiding axis
  18. 根据权利要求17的离子导引装置,其特征在于,所述离子导引通道内的电场强度沿导引轴呈周期性变化。 The ion guiding device according to claim 17, wherein the electric field intensity in said ion guiding channel changes periodically along the guiding axis.
  19. 根据权利要求2的离子导引装置,其特征在于,各细丝以焊接、缠绕或夹紧的方式固定在所述悬拉支架上。 The ion guiding device according to claim 2, wherein each of the filaments is fixed to the suspension holder by welding, winding or clamping.
  20. 根据权利要求2的离子导引装置,其特征在于,所述悬拉支架上具有穿线孔和印刷电路。 The ion guiding device according to claim 2, wherein said suspension bracket has a threading hole and a printed circuit.
  21. 根据权利要求2的离子导引装置,其特征在于进一步包括安装于所述悬拉支架上的弹性材料做成的绷紧机构。The ion guiding device according to claim 2, further comprising a tensioning mechanism made of an elastic material attached to said suspension bracket.
  22. 根据权利要求2的离子导引装置,其特征在于,至少部分细丝的悬拉支架构成离子导引装置的外壁。The ion guiding device according to claim 2, wherein at least a portion of the filaments of the suspension stent constitute an outer wall of the ion guiding device.
  23. 根据权利要求22的离子导引装置,其特征在于,所述离子导引装置的外壁上有排气孔。The ion guiding device according to claim 22, wherein said ion guiding means has an exhaust hole on an outer wall thereof.
  24. 根据权利要求1的离子导引装置,其特征在于,所述导引轴为曲线形导引轴。The ion guiding device according to claim 1, wherein said guiding shaft is a curved guiding shaft.
  25. 根据权利要求24的离子导引装置,其特征在于,进一步包括直流电压提供装置,使至少其中一部分层细丝电极的细丝之间叠加一个直流电压,以帮助离子沿着曲线形导引轴偏转。The ion guiding device according to claim 24, further comprising DC voltage supply means for superimposing a direct current voltage between the filaments of at least a portion of the layer of the filament electrodes to assist in deflecting the ions along the curved guiding axis .
  26. 根据权利要求10的离子导引装置,其特征在于,所述的高频电压源包括多个高频高压开关,以产生矩形波高频电压。The ion guiding apparatus according to claim 10, wherein said high frequency voltage source comprises a plurality of high frequency high voltage switches to generate a rectangular wave high frequency voltage.
  27. 根据权利要求14的离子导引装置,其特征在于,所述导引轴方向的电位梯度所引起的离子迁移运动方向与轴向气流方向相反,使仅有特定离子迁移率的一部分离子得到有效传输。The ion guiding device according to claim 14, wherein the direction of the ion migration caused by the potential gradient in the direction of the guiding axis is opposite to the direction of the axial gas flow, so that a part of ions having only a specific ion mobility are efficiently transmitted. .
  28. 根据权利要求10的离子导引装置,其特征在于,至少一部分层细丝电极中细丝的间距设置以及高频电压设置使进入离子导引装置的离子在此部分细丝所在空间的附近实现具有质量选择性的通过,阻挡或消灭。The ion guiding device according to claim 10, wherein the spacing of the filaments in at least a portion of the layer of filament electrodes and the setting of the high frequency voltage enable ions entering the ion guiding device to be realized in the vicinity of the space in which the filaments are located Passivity, pass or eliminate.
  29. 根据权利要求14的离子导引装置,其特征在于,所述高频电压的设置以及所述导引轴方向的电位梯度设置使进入离子导引装置的离子与中性气体分子发生有效碰撞,并使碰撞反应后生成的产物离子、碎片离子、或去溶剂化的离子得到有效地传输。The ion guiding device according to claim 14, wherein said setting of said high frequency voltage and said potential gradient setting of said guiding axis direction cause an ion entering the ion guiding device to collide with a neutral gas molecule, and The product ions, fragment ions, or desolvated ions generated after the collision reaction are efficiently transported.
  30. 根据权利要求1或2的离子导引装置,其特征在于,所述离子导引装置的至少一部分存在流动的气体,所述流动气体的气压范围在10至10000帕斯卡之间。The ion guiding device according to claim 1 or 2, wherein at least a portion of said ion guiding means has a flowing gas, and said flowing gas has a gas pressure ranging between 10 and 10,000 Pascals.
  31. 根据权利要求1或2的离子导引装置,其特征在于,所述细丝的直径小于0.5mm。The ion guiding device according to claim 1 or 2, wherein the filament has a diameter of less than 0.5 mm.
  32. 根据权利要求1的离子导引装置,其特征在于,所述离子导引装置的至少一部分细丝电极还作为加热器。The ion guiding device of claim 1 wherein at least a portion of the filament electrode of said ion guiding device also functions as a heater.
  33. 一种离子导引装置组合结构,包括多个如权利要求1所述的离子导引装置的组合,其中所述多个离子导引装置共用至少一部分细丝。An ion guiding device assembly comprising a plurality of combinations of ion guiding devices according to claim 1 wherein said plurality of ion guiding devices share at least a portion of the filaments.
  34. 一种离子导引装置组合结构,包括多个如权利要求1所述的离子导引装置的组合,其中所述组合结构中存在离子导引装置的导引轴的汇聚、发散或重合。 An ion guiding device assembly comprising a plurality of combinations of ion guiding devices according to claim 1 wherein there is convergence, divergence or coincidence of the guiding axes of the ion guiding devices.
PCT/CN2012/070709 2012-01-21 2012-01-21 Ion guide device WO2013107060A1 (en)

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Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5206506A (en) * 1991-02-12 1993-04-27 Kirchner Nicholas J Ion processing: control and analysis
CN102339719A (en) * 2010-07-29 2012-02-01 岛津分析技术研发(上海)有限公司 Ion guide device

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5206506A (en) * 1991-02-12 1993-04-27 Kirchner Nicholas J Ion processing: control and analysis
CN102339719A (en) * 2010-07-29 2012-02-01 岛津分析技术研发(上海)有限公司 Ion guide device

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