WO2012132550A1 - 飛行時間型質量分析装置 - Google Patents
飛行時間型質量分析装置 Download PDFInfo
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- WO2012132550A1 WO2012132550A1 PCT/JP2012/052593 JP2012052593W WO2012132550A1 WO 2012132550 A1 WO2012132550 A1 WO 2012132550A1 JP 2012052593 W JP2012052593 W JP 2012052593W WO 2012132550 A1 WO2012132550 A1 WO 2012132550A1
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- ion
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- mass spectrometer
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/02—Details
- H01J49/06—Electron- or ion-optical arrangements
- H01J49/067—Ion lenses, apertures, skimmers
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
- H01J49/00—Particle spectrometers or separator tubes
- H01J49/26—Mass spectrometers or separator tubes
- H01J49/34—Dynamic spectrometers
- H01J49/40—Time-of-flight spectrometers
- H01J49/401—Time-of-flight spectrometers characterised by orthogonal acceleration, e.g. focusing or selecting the ions, pusher electrode
Definitions
- the present invention relates to a time-of-flight mass spectrometer, and more particularly, to an ion injection optical system for injecting ions to an orthogonal acceleration unit in a time-of-flight mass spectrometer of an orthogonal acceleration method (also referred to as a vertical acceleration method).
- TOFMS time-of-flight mass spectrometer
- a constant kinetic energy is applied to ions derived from sample components to fly in a space of a certain distance, and the time required for the flight is measured and the time of flight is measured. From this, the mass-to-charge ratio of ions is obtained. Therefore, one of the major factors that lower the mass resolution in TOFMS is the initial energy variation of ions.
- the reflectron type TOFMS the reflectron has a function of correcting a difference in kinetic energy.
- turnaround time is another factor that deteriorates mass resolution.
- the turnaround time means that when an ion is accelerated in the time-of-flight analysis direction, an ion having a velocity component in a direction opposite to the time-of-flight analysis direction starts from the ion due to the initial energy of the ion, and then the start point. This is the time required to return to the point of time, and is the difference in flight time between ions having velocity components in the reverse direction and ions having velocity components in the forward direction with respect to the flight time analysis direction. Therefore, in a broad sense, this turnaround time is due to variations in the initial energy of ions, but errors due to the turnaround time cannot be corrected by the reflectron. Therefore, how to reduce the influence of turnaround time in improving the mass resolution of TOFMS is an important issue.
- FIG. 11 is a schematic configuration diagram of an ion orthogonal acceleration unit of the orthogonal acceleration method TOFMS and an ion incident optical system in the preceding stage.
- the orthogonal acceleration unit 4 includes a flat plate electrode 41 and a mesh electrode 42 formed with a large number of openings through which ions can pass, and the ion incidence optical system 300 includes two slit plates (separated by a predetermined gap L). Or an aperture plate) 301 and 302.
- the initial beam direction of the ion beam incident on the acceleration region sandwiched between the electrodes 41 and 42 is the X direction
- the acceleration direction, that is, the time-of-flight analysis direction is the Z direction orthogonal to the X direction.
- the electrodes 41 and 42 are at the same potential (for example, ground potential), and there is no electric field in the acceleration region.
- the flight time spread in the orthogonal acceleration unit 4 will be considered.
- E and ⁇ are the energy of the ion beam incident on the orthogonal acceleration region and the angle formed with the X axis.
- the greater the initial energy Ez the greater the flight time spread due to the turnaround time described above.
- the beam limiting mechanism is for limiting the angle ⁇ to be small. In the example of FIG.
- the angular spread ⁇ of the beam with respect to the gap L between the two slit plates 301 and 302 and the opening width h of the slit plate 302. Is given by tan -1 (h / L). Therefore, by appropriately setting the gap L and the opening width h, the angle ⁇ of the ion beam can be suppressed, and variations in initial energy of ions can be kept within an allowable range.
- an electrostatic lens that is an aperture lens is disposed between the ion trap and the beam limiting mechanism in order to efficiently introduce ions emitted from the ion trap into the beam limiting mechanism.
- an electrostatic lens with an aperture lens and a beam limiting mechanism composed of two slit plates is widely used in actual devices.
- the conventional configuration as described above has the following problems.
- a substantial part of the ion beam bundle hits the slit plate and is blocked. Therefore, the amount of ions actually used for the time-of-flight analysis is considerably reduced from the original amount of ions, and it is inevitable that the measurement sensitivity is lowered.
- the beam angle ⁇ increases and the mass resolution decreases.
- the present invention has been made to solve the above-mentioned problems, and the main object of the present invention is to increase the angle spread by reducing the angular spread without losing the beam intensity as much as possible when ions are fed into the orthogonal acceleration unit.
- An object of the present invention is to provide an orthogonal acceleration type time-of-flight mass spectrometer capable of realizing mass resolution and high measurement sensitivity.
- Another object of the present invention is to provide an orthogonal acceleration time-of-flight mass spectrometer capable of easily switching between measurement focusing on mass resolution and measurement focusing on measurement sensitivity in accordance with the analysis purpose and the like. There is.
- the present inventor proposed Heddle as an ion incident optical system for sending ions to an orthogonal acceleration unit (see Non-Patent Documents 2 and 3) and two front and rear lenses in the electrostatic lens.
- the idea was to use a combination with a diaphragm placed on the common focal plane of the virtual convex lens.
- the present invention made to solve the above problems includes an orthogonal acceleration unit that accelerates incident ions in a direction perpendicular to the incident axis, an ion incident optical system that sends ions to the orthogonal acceleration unit,
- the ion incidence optical system is a) an electrostatic lens composed of five or more cylindrical electrodes arranged along the ion optical axis; b) voltage applying means for applying a voltage to each of the cylindrical electrodes so that the electrostatic lens is an afocal system; c) A hypothetical virtual stage formed by a part of the five or more cylindrical electrodes under a state in which a voltage is applied by the voltage applying unit so that the electrostatic lens becomes an afocal system.
- An aperture means having an aperture of a predetermined size on the ion optical axis, disposed on a common focal plane of a convex lens and a virtual convex lens at a later stage formed by a part of electrodes of the five or more cylindrical electrodes; It is characterized by having.
- an ion beam incident parallel to the optical axis of the electrostatic lens has an optical axis on the common focal plane. Passes and exits parallel to the optical axis.
- the ion beam incident non-parallel to the optical axis passes through a position shifted from the optical axis on the common focal plane. Therefore, the angular spread of the emitted ion beam is determined according to the size of the aperture of the aperture means.
- the spatial spread of the outgoing ion beam is determined by the focal length of the two front and rear virtual convex lenses, it can be determined independently of the angular spread of the outgoing ion beam.
- the angular spread can be limited without substantially affecting the spatial spread of the outgoing ion beam.
- the conventional beam limiting mechanism combining two slits effectively uses the ion beam shielded by the slit, that is, as an outgoing ion beam. Since it can be reflected, mass resolution can be increased while maintaining a certain level of measurement sensitivity.
- the electrostatic lens when the electrostatic lens is an afocal system, a beam parallel to the optical axis of the electrostatic lens is emitted in parallel, but this state is the same as that of the diaphragm means placed on the common focal plane. It does not mean that the amount of ions passing through the aperture is maximized. That is, in general, the ion passing efficiency is maximized in the electrostatic lens when the electrostatic lens is a non-afocal system, and at that time, the angular spread of the emitted ion beam is not minimized.
- the voltage application means applies a voltage to each of the cylindrical electrodes so that the electrostatic lens is a predetermined non-afocal system deviating from afocal conditions. And by changing the setting of the voltage applied from the voltage application means to the cylindrical electrode, the operation mode prioritizing mass resolution and the operation mode prioritizing sensitivity can be switched. Good.
- the aperture shape of the aperture means is generally a circular shape that is rotationally symmetric about the ion optical axis.
- the spatial spread of the ions is as narrow as possible in the acceleration direction (time-of-flight analysis direction). If ions are spread to some extent, the amount of ions used for analysis increases, which is advantageous in terms of sensitivity. That is, the preferred state of spatial expansion of ions is different in two directions along two axes orthogonal to each other in a plane orthogonal to the ion optical axis.
- the aperture shape of the aperture means may be a rectangle or an ellipse centered on the ion optical axis, that is, the aperture size may be different in the direction along two axes perpendicular to each other. preferable.
- the shape of the ion incident aperture formed at the front edge of the first cylindrical electrode located closest to the entrance among the plurality of cylindrical electrodes constituting the electrostatic lens is generally circular. However, for the above reason, it is preferable that the shape of the ion incident aperture is rectangular or elliptical.
- the shape of the leading edge of the first-stage cylindrical electrode located closest to the entrance among the plurality of cylindrical electrodes constituting the electrostatic lens is at the top.
- a skimmer shape in which an ion incident opening is formed is preferable.
- the electrostatic lens is the center of the preceding virtual convex lens formed in a state where the electrostatic lens is driven to be an afocal system.
- the distance between the object point and the object point and the distance between the center of the latter virtual convex lens formed in the same state and the image point may be the same symmetrical arrangement. In the case of such a symmetrical arrangement, it is only necessary to apply the same voltage to the cylindrical electrode constituting the upstream virtual convex lens and the cylindrical electrode constituting the downstream virtual convex lens, and therefore, the advantage that voltage adjustment is easy, etc. There is.
- the electrostatic lens is formed in a state where the electrostatic lens is driven so that the electrostatic lens becomes an afocal system.
- the distance between the center of the lens and the object point may be different from the distance between the center of the subsequent virtual convex lens formed in the same state and the image point.
- the distance from the center of the virtual convex lens in the subsequent stage to the image point is increased, the distance from the object point to the center of the virtual convex lens in the previous stage is also increased, so the total length of the electrostatic lens is increased.
- the distance from the center of the virtual convex lens at the rear stage to the image point can be increased, while the distance from the object point to the center of the virtual convex lens at the front stage can be shortened. It is advantageous to suppress
- the voltage applying means applies a voltage to each of the plurality of cylindrical electrodes so that the ions are accelerated or decelerated before and after the ions pass through the electrostatic lens. It is good also as a structure to apply. If the energy of the ions incident on the electrostatic lens is too large, the ions are decelerated (decreasing energy) in the process of passing through the electrostatic lens and sent to the orthogonal acceleration unit. It is possible to suppress the initial energy Ez in the time-of-flight analysis direction of ions accelerated by.
- time-of-flight mass spectrometer According to the time-of-flight mass spectrometer according to the present invention, it is possible to reduce the angular spread of ions while sufficiently securing the amount of ions incident on the orthogonal acceleration unit as compared with the conventional apparatus. Thereby, high mass resolution can be achieved while suppressing a decrease in measurement sensitivity.
- the user can easily perform “high resolution measurement mode” in which mass resolution is prioritized according to the purpose of analysis and measurement sensitivity. Can be switched to the “high sensitivity measurement mode”. As a result, it is possible to perform an accurate analysis according to the purpose of analysis and the type of sample.
- FIG. 2 is an overall configuration diagram of the orthogonal acceleration type TOFMS of this embodiment
- FIG. 1 is a schematic configuration diagram (a) of the ion incidence optical system in the orthogonal acceleration type TOFMS, and optical equivalent configuration diagrams (b) and (c) thereof. It is.
- the orthogonal acceleration type TOFMS includes an ion source 1 that ionizes a target sample, a TOF analyzer 5 that includes a reflector 51, an orthogonal acceleration unit 4 that accelerates ions and sends them to the TOF analyzer 5, and an ion source.
- an electrostatic lens 3 that sends ions emitted from 1 to the orthogonal acceleration unit 4, a detector 6 that detects ions flying in the flight space of the TOF analyzer 5, and data obtained by the detector 6
- a data processing unit 16 that creates a mass spectrum and the like, an electrostatic lens power source unit 12 that applies a predetermined voltage to each electrode constituting the electrostatic lens 3, and an electrode 41 included in the orthogonal acceleration unit 4 42, the orthogonal acceleration power supply unit 13 for applying a predetermined voltage to 42, the reflector power supply unit 14 for applying a predetermined voltage to the reflector 51, the control unit 15 for controlling the operation of each unit, the analysis conditions, etc.
- It comprises an input unit 17, a.
- the ionization method in the ion source 1 is not particularly limited.
- an atmospheric pressure ionization method such as an electrospray ionization (ESI) method or an atmospheric pressure chemical ionization (APCI) method is used.
- ESI electrospray ionization
- APCI atmospheric pressure chemical ionization
- MALDI matrix assisted laser desorption ionization
- ions emitted from the acceleration region of the orthogonal acceleration unit 4 are turned back by an electric field formed by a voltage applied from the reflector power supply unit 14 to the reflector 51, and finally the detector.
- the detector 6 generates a detection signal corresponding to the amount of ions that have arrived, and the data processor 16 obtains a time-of-flight spectrum from this detection signal, and further obtains a mass spectrum by converting the time of flight to a mass-to-charge ratio.
- apparatus components having a relatively high gas pressure such as an ion source and a collision cell, are arranged in front of the electrostatic lens 3, so in this example, the inflow of gas into the electrostatic lens 3 is prevented.
- the front edge of the cylindrical electrode 31 at the first stage is formed in a skimmer shape, and the ion incident opening 36 is provided at the top, but it is not always necessary to have the skimmer shape.
- a common voltage V1 is applied to the three cylindrical electrodes 31, 33, and 35 in the first, third, and last stages, and the two cylindrical electrodes in the second and fourth stages.
- a common voltage V2 different from the voltage V1 is applied to 32 and 34.
- the two cylindrical electrodes 32 and 34 in the second and fourth stages are sufficiently short in the direction of the ion optical axis C compared to the cylindrical electrode 33 sandwiched between them.
- a virtual convex lens (hereinafter referred to as “front-side virtual convex lens”) L1 is formed by the field, and the rear edge of the third-stage cylindrical electrode 33 and the last-stage cylindrical shape centering on the fourth-stage cylindrical electrode 34.
- Another virtual convex lens (hereinafter referred to as “back side virtual convex lens”) L ⁇ b> 2 is formed by a DC electric field formed by the front edge portion of the electrode 35.
- the angular spread of the outgoing beam is determined by the size (diameter) of the aperture 39.
- the electrostatic lens 3 composed of a plurality of cylindrical electrodes 31 to 35 as in this embodiment and the beam restriction as shown in FIG.
- the configuration of the present embodiment can pass more ion beams by the action of the front-side virtual convex lens L1 and the rear-side virtual convex lens L2 as described above. Therefore, the configuration of the electrostatic lens 3 is advantageous in increasing the measurement sensitivity because more ions can be sent to the orthogonal acceleration unit 4 while suppressing the angular spread and spatial spread of the emitted beam.
- the electrostatic lens 3 becomes a non-afocal system. It is possible to maximize the amount of ions passing through the aperture 39 when a certain predetermined voltage is applied. Generally, as shown in FIG. 1C, this is because the ion beam incident so as to intersect the ion optical axis C at a predetermined angle with respect to the ion optical axis C at the ion incident aperture 36 is installed on the aperture plate 38. In this state, the characteristics of the virtual convex lenses L1 and L2 are adjusted so as to converge at a position (gather on the ion optical axis C). At this time, since the maximum amount of ions can be fed into the orthogonal acceleration unit 4, the measurement sensitivity is good, but the angular spread of the outgoing beam becomes large, so the mass resolution is sacrificed to some extent.
- FIG. 3 shows the result of calculating the ion trajectory with [mm] and 5 types of ion beam incident angles (angles formed with the ion optical axis C) of ⁇ 10, ⁇ 5, 0, 5, 10 [deg]. It can be seen from the ion trajectory shown in FIG. 3 that only the angular spread can be effectively limited without substantially affecting the spatial spread of the ion beam by placing the aperture stop on the common focal plane.
- an ion trajectory was simulated under afocal conditions and non-afocal conditions (maximum signal intensity) when the size of the aperture 39 was determined to be a predetermined value.
- the initial energy of ions is 10 [eV]
- 1000 ions (m / z 1000) are arranged on the ion incident aperture 36 (see FIG. 4A). Under this condition, the objective is to suppress the angular spread of the ion beam to ⁇ 2 [deg] or less on the ion emission aperture 37, and referring to FIG. I decided.
- FIG. 4 (b) shows the result of calculating the ion trajectory under the afocal condition. Specifically, the voltage V1 of the cylindrical electrodes 31, 33, and 35 is 0V, and the voltage V2 of the cylindrical electrodes 32 and 34 is ⁇ 30V. At this time, the number of ions that can pass through the electrostatic lens 3 is 275/1000.
- the same initial trajectory is set, and the voltage applied to the electrostatic lens 3 is set so as to be a non-afocal system (that is, “high sensitivity measurement mode”) having the maximum ion passage rate, and the same trajectory.
- the voltage V1 of the cylindrical electrodes 31, 33, and 35 is 0V
- the voltage V2 of the cylindrical electrodes 32 and 34 is ⁇ 110V.
- FIG. 4C As can be seen from FIG. 4C, at this time, the ion beam forms a beam waist at the position of the aperture opening 39. At this time, many ions can pass (967/1000).
- FIG. 5 A histogram showing the Z-direction spatial distribution (a) and the angular spread distribution (b) of ions incident on the detector installed on the ion emission opening 37 at this time is shown in FIG. As can be seen from a comparison with FIG. 5, in this case, since the angular spread is large, the energy spread in the TOF discharge direction is large, so that the mass resolution is lowered.
- the “high resolution measurement mode” and the “high sensitivity measurement mode” can be switched only by changing the voltage applied to the cylindrical electrodes 32 and 34. It can be performed. This switching is very simple since it is sufficient to simply switch the voltage set in advance in the electrostatic lens power supply unit 12 and there is no mechanical switching or replacement other than that, and the switching can be performed during measurement. Is possible. Therefore, for example, when measuring a target component whose concentration (content) is unknown, the measurement is first performed in the “high sensitivity measurement mode” at the expense of mass resolution.
- the mode can be switched to the “high resolution measurement mode” to obtain a mass spectrum with a high mass resolution.
- the “high resolution measurement mode” it is also possible to switch from the “high resolution measurement mode” to the “high sensitivity measurement mode”.
- the sensitivity and resolution are continuously changed, the sensitivity and resolution are changed stepwise, and discontinuous.
- Various changes such as changing the sensitivity and resolution are possible.
- FIG. 7A is a schematic configuration diagram showing an electrostatic lens 3B and an orthogonal acceleration unit 4 of another embodiment
- FIG. 7B is an optical equivalent configuration diagram.
- symbol is attached
- an ion source 1 is arranged as in the configuration example shown in FIG. 2, or a collision cell is arranged in the case of an MS / MS mass spectrometer. All the elements are in a state where the gas pressure is high (the degree of vacuum is low).
- the gas pressure inside the electrostatic lens is sufficiently low, that is, the density of residual gas molecules is sufficiently low.
- the orthogonal acceleration unit 4 and the TOF analyzer 5 in the subsequent stage are also required to have a sufficiently low gas pressure (high degree of vacuum).
- the gas conductance is reduced by reducing the ion incident aperture 36 in the first-stage cylindrical electrode 31 to ⁇ 1.6 [mm].
- ions are accelerated and collected at the tip of the sharp skimmer, thereby reducing the initial angular spread of ions passing through the ion incident aperture 36. If the initial angular spread of ions is extremely large, adding one or more lenses before the electrostatic lens 3B reduces the initial angle of ions, thereby avoiding a decrease in ion intensity. To be able to.
- the image point I is located at the ion emission opening 37 of the cylindrical electrode 35 at the final stage of the electrostatic lens 3, but when the ions are accelerated by the orthogonal acceleration unit 4, In order to reduce the ion space spread, it is desirable that the image point I comes to the center of the orthogonal acceleration unit 4 as shown in FIG.
- the orthogonal acceleration unit 4 generally includes a large number of ring-shaped guard ring electrodes 43 as shown in FIG. 7A, the diameter of the orthogonal acceleration unit 4 in the X direction cannot be ignored, and the normal number About 10 mm is required. Therefore, a lens having a long distance from the center to the image point I is required as the rear-side virtual convex lens L2.
- the distance from the object point O to the center of the front-side virtual convex lens L1 is the same as the distance from the center of the rear-side virtual convex lens L2 to the image point I.
- the asymmetric arrangement as in the present embodiment is suitable for keeping the total length of the electrostatic lens 3B as small as possible while ensuring the distance from the center of the rear-stage side virtual convex lens L2 to the center of the orthogonal acceleration unit 4 as large as possible.
- Angular spread limitation For high mass resolution, it is necessary to limit the angular spread of ions in the time-of-flight analysis direction (Z direction) to a very small limit. On the other hand, it is not necessary to restrict the angular spread of ions in the Y direction orthogonal to the X direction and the Z direction, which are the ion incident directions, as severely as the Z direction. Rather, in order to increase the signal intensity by increasing the amount of ions that reach the detector, the angle limit in the Y direction is loose within a range that can affect the spread of ions arriving at the detector and the mass resolution. Is preferred.
- the electrostatic lens can set the angular spread of ions in the Y and Z directions independently.
- the position (space) spread of ions in the Z direction causes an energy spread of an ion packet to be subjected to mass analysis, and thus is preferably small.
- the spatial expansion of ions in the Y direction need not be restricted as severely as the Z direction. Rather, as with the angular spread, in order to increase the signal intensity, it is preferable that the limit of the spatial spread of ions in the Y direction is also loose within an allowable range. Therefore, in the electrostatic lens, it is desirable that the spatial spread of ions in the Y direction and the Z direction can be set independently.
- the aperture opening 39 of the aperture plate 38 disposed on the inner periphery of the central cylindrical electrode 33 is different in the Y direction and the Z direction.
- a shape having a length is preferable. Specifically, for example, a rectangle or an ellipse.
- a simulation performed to confirm the effect of making the shape of the aperture opening 39 not a circle but a rectangle or an ellipse will be described.
- the configuration assumed in the simulation is the electrode arrangement shown in FIG. 7A, and the aperture 39 has a rectangular shape of 9 [mm] (Y direction) ⁇ 3.4 [mm] (Z direction).
- the object point O is set as an ion (m / z1000, initial energy 26 [eV]) emission position, and the ion is emitted by changing the initial angle of the ion (angle from the X direction (ion optical axis C)) within a predetermined range.
- the ion trajectory was calculated.
- FIG. 8 is a perspective sectional view showing ion trajectories under afocal conditions in which the voltages applied to the five cylindrical electrodes 31 to 35 are 0 V, ⁇ 61 V, 0 V, ⁇ 61 V, and 0 V in order from the entrance side. It is.
- (A) is the Z direction
- (b) is the Y direction
- the initial angles of ⁇ 5 to 5 [deg] and 0.1 [deg] steps are given, and 101 ion trajectories are calculated and depicted. It is a result.
- the ion angle spread in the Y direction and the Z direction can be set independently by using the rectangular aperture 39 that is elongated in the Y direction.
- the shape of the aperture opening 39 is not limited to a rectangle, but may be an elliptical shape with a different aspect ratio.
- FIG. 9 shows the result of the simulation considering the initial position spread of the ions at the object point O.
- the drawing is drawn by stretching in the vertical direction so that the difference in the ion trajectory due to the difference in the initial position and the initial angle of the ions becomes clear.
- 21 ion trajectories are drawn with initial angles of ⁇ 5 to 5 [deg] and 0.5 [deg] steps. It can be seen that the diaphragm opening 39 discriminates not only by the difference in the initial position of ions but by the difference in the initial angle, and effectively limits the angular spread of ions.
- the aperture opening 39 having the shape used here can limit the ion angle spread within about ⁇ 1.5 [deg] in the Z direction and within about ⁇ 4 [deg] in the Y direction.
- the shape (size) of the aperture opening 39 By changing the shape (size) of the aperture opening 39, the angular spread in the Z direction and the Y direction can be set independently, and while limiting the ion angular spread in the Z direction required for high mass resolution, Y Sensitivity can be improved by relaxing the ion angular spread in the direction.
- a light beam (ion flux) emitted from the entrance (object point O) of the afocal electrostatic lens 3 forms an image at the center (image point I) of the orthogonal acceleration unit 4. .
- the shape of the entrance of the electrostatic lens 3, that is, the ion incident opening 36 is preferably not a circular shape but a shape wider in the Y direction than the Z direction, such as a rectangular shape or an elliptical shape.
- FIG. 10 shows a simulation result under a non-afocal condition in which the applied voltage value to each of the cylindrical electrodes 31 to 35 is adjusted so as to form an image at the center of the stop aperture 39 and the orthogonal acceleration unit 4, respectively.
- the extraction conditions such as the initial angle of ions are the same as in the simulation of FIG.
- the voltage values applied to the cylindrical electrodes 32 and 34 that are the centers of the two virtual convex lenses are not the same.
- the applied voltages to the five cylindrical electrodes 31 to 35 are 0 V, ⁇ 215 V, 0 V, ⁇ 135 V, and 0 V in order from the entrance.
- FIG. 10 although the angular spread of ions at the center of the orthogonal acceleration unit 4 increases, ions can be transported to the orthogonal acceleration unit 4 with almost no loss of ion intensity. Thereby, a larger amount of ions can be subjected to mass spectrometry and the sensitivity can be improved.
- the electrostatic lenses 3 and 3B are configured by the five cylindrical electrodes 31 to 35, but the electrostatic lens may be configured by six or more cylindrical electrodes.
- the electrostatic lens may be configured by six or more cylindrical electrodes.
- ions when ions are directly incident on the electrostatic lenses 3 and 3B from the ion source 1, it is predicted that the ions have a significantly large angular spread. In that case, it is advisable to add one or more cylindrical electrodes in front of the five cylindrical electrodes described in the above embodiment to suppress the angular spread of ions.
- a configuration may be adopted in which ions emitted from the ion source 1 such as an ESI ion source are directly introduced into the electrostatic lenses 3 and 3B, or between the ion source 1 and the electrostatic lens 3, a linear type or A three-dimensional quadrupole ion trap may be arranged so that ions are once held by the ion trap and then ions emitted from the ion trap are introduced into the electrostatic lenses 3 and 3B.
- a Q-TOF type device configuration in which Q1 and Q2 (collision cells) of a triple quadrupole mass spectrometer are arranged in front of the electrostatic lens may be used. That is, the components arranged in the previous stage of the electrostatic lenses 3 and 3B are not particularly limited.
- the energy of the ions may be too large.
- by decelerating the ions in the electrostatic lens and dropping the energy low energy ions can be sent to the orthogonal acceleration part, which is effective in suppressing the initial ion energy in the direction of TOF analysis in the orthogonal acceleration part. It is.
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Abstract
Description
イオンがもつ飛行時間分析方向の初期エネルギEzは、Ez=Esin2αで与えられる。ここで、E及びαは直交加速領域に入射してくるイオンビームのエネルギ及びX軸となす角度である。初期エネルギEzが大きいほど、前述のターンアラウンドタイムによる飛行時間広がりは大きくなる。初期エネルギEzを小さくするためには、エネルギE及び角度αを小さくする必要がある。ビーム制限機構はこの角度αを小さく制限するためのものであり、図11の例の場合、2枚のスリット板301、302の間隙L及びスリット板302の開口幅hに対しビームの角度広がりαはtan-1(h/L)で与えられる。したがって、間隙L、開口幅hを適切に設定することでイオンビームの角度αを抑え、イオンがもつ初期エネルギのばらつきを許容範囲内に収めることができる。
上記ビーム制限機構では、イオンビーム束のかなりの部分がスリット板に当たって遮蔽される。そのため、実際に飛行時間分析に供されるイオンの量は元のイオン量からかなり減じてしまい、測定感度が下がることが避けられない。また、測定感度を上げるためにはスリットの開口幅hを広げる必要があるが、そうするとビームの角度αが大きくなって質量分解能が下がることになる。このように、質量分解能と測定感度とはトレードオフの関係にあり、高質量分解能を実現するためには測定感度を犠牲にせざるをえなかった。
また、本発明の別の目的は、分析目的等に応じて質量分解能を重視した測定と測定感度を重視した測定とを容易に切り替えることができる直交加速方式の飛行時間型質量分析装置を提供することにある。
前記イオン入射光学系は、
a)イオン光軸に沿って配置された5個以上の円筒状電極からなる静電レンズと、
b)前記静電レンズがアフォーカル系となるように前記円筒状電極にそれぞれ電圧を印加する電圧印加手段と、
c)前記静電レンズがアフォーカル系となるように前記電圧印加手段により電圧が印加されている状態の下で、前記5個以上の円筒状電極の一部の電極により形成される前段の仮想凸レンズと該5個以上の円筒状電極の一部の電極により形成される後段の仮想凸レンズとの共通の焦点面に配置された、イオン光軸上に所定サイズの開口を有する絞り手段と、
を備えることを特徴としている。
こうした対称配置である場合には、前段の仮想凸レンズを構成する円筒状電極と後段の仮想凸レンズを構成する円筒状電極とに同一電圧を印加すればよいので、電圧調整が容易である等の利点がある。
直交加速方式TOFMSでこうした静電レンズを用いる場合、直交加速部の中心付近に像点を位置させる必要があることから、後段の仮想凸レンズの中心から像点までの距離を充分に長く確保する必要がある。上述した対称配置では、後段の仮想凸レンズの中心から像点までの距離を長くすると物点から前段の仮想凸レンズの中心までの距離も等しく長くなるため、静電レンズの全長が長くなる。これに対し、非対称配置では、後段の仮想凸レンズの中心から像点までの距離を長くする一方、物点から前段の仮想凸レンズの中心までの距離を短くすることができるので、静電レンズの全長を抑えるのに有利である。
例えば、イオンを生成するイオン源から出射されたイオンが直接、静電レンズに導入される構成としてもよいし、イオン源と静電レンズとの間に別のイオンガイドを設ける構成としてもよい。また、静電レンズの前段にイオンの解離を促進するコリジョンセルが配置され、該コリジョンセルで生成されたフラグメントイオンが静電レンズに導入される構成としてもよい。さらには、静電レンズの前段にイオンを保持する機能を有するイオントラップが配置され、該イオントラップから出射されたイオンが静電レンズに導入される構成としてもよい。イオントラップはリニア型イオントラップ、三次元四重極型イオントラップのいずれでもよい。
(1)角度広がり制限:高質量分解能のためには、飛行時間分析方向(Z方向)のイオンの角度広がりをごく小さく制限する必要がある。一方、イオン入射方向であるX方向とZ方向とに直交するY方向へのイオンの角度広がりはZ方向ほど厳しく制限する必要はない。むしろ、検出器に到達するイオンの量を増やすことで信号強度を大きくするには、Y方向の角度制限は、検出器へ到着するイオンの広がりや質量分解能への影響が許される範囲内で緩い方が好ましい。こうしたことから、静電レンズではY方向とZ方向のイオンの角度広がりを独立に設定できることが望ましい。
(2)位置広がり制限:Z方向へのイオンの位置(空間)広がりは、質量分析の対象となるイオンパケットのエネルギ広がりを引き起こすので小さい方が望ましい。一方、Y方向へのイオンの空間広がりは、Z方向ほど厳しく制限する必要はない。むしろ、角度広がりと同様に、信号強度を大きくするためにはY方向へのイオンの空間広がりの制限も許容範囲内で緩い方が好ましい。したがって、静電レンズではY方向とZ方向のイオンの空間広がりも独立に設定できることが望ましい。
また、本発明に係るTOFMSはTOF分析器がリフレクトロン型に限らずリニア型等でも構わない。また、例えばESIイオン源等のイオン源1から発したイオンを直接的に静電レンズ3、3Bに導入する構成でもよいし、またイオン源1と静電レンズ3との間に、リニア型又は三次元四重極型のイオントラップを配置し、イオントラップで一旦イオンを保持したあとに該イオントラップから出射したイオンを静電レンズ3、3Bに導入する構成としてもよい。さらにまた、静電レンズの前段に三連四重極型質量分析装置のQ1及びQ2(コリジョンセル)を配置するQ-TOF型の装置構成であってもよい。即ち、静電レンズ3、3Bの前段に配置される構成要素は特に限定されない。
2…イオンガイド
3、3B…静電レンズ
31~35…円筒状電極
36…イオン入射開口
37…イオン出射開口
38…アパーチャ板
39…絞り開口
L1、L2…仮想凸レンズ
4…直交加速部
41…平板電極
42…メッシュ状電極
43…ガードリング電極
5…TOF分析器
51…反射器
6…検出器
12…静電レンズ電源部
13…直交加速電源部
14…反射器電源部
15…制御部
16…データ処理部
17…入力部
C…イオン光軸
Claims (14)
- 入射してきたイオンをその入射軸と直交する方向に加速する直交加速部と、該直交加速部へイオンを送り込むイオン入射光学系と、を具備する直交加速方式の飛行時間型質量分析装置において、
前記イオン入射光学系は、
a)イオン光軸に沿って配置された5個以上の円筒状電極からなる静電レンズと、
b)前記静電レンズがアフォーカル系となるように前記円筒状電極にそれぞれ電圧を印加する電圧印加手段と、
c)前記静電レンズがアフォーカル系となるように前記電圧印加手段により電圧が印加されている状態の下で、前記5個以上の円筒状電極の一部の電極により形成される前段の仮想凸レンズと該5個以上の円筒状電極の一部の電極により形成される後段の仮想凸レンズとの共通の焦点面に配置された、イオン光軸上に所定サイズの開口を有する絞り手段と、
を備えることを特徴とする飛行時間型質量分析装置。 - 請求項1に記載の飛行時間型質量分析装置であって、
前記電圧印加手段は前記静電レンズがアフォーカル条件からずれた所定の非アフォーカル系となるように前記円筒状電極にそれぞれ電圧を印加可能であり、該電圧印加手段から前記円筒状電極に印加する電圧の設定を変更することにより、質量分解能を優先させる動作モードと感度を優先させる動作モードとを切り替え可能であることを特徴とする飛行時間型質量分析装置。 - 請求項1又は2に記載の飛行時間型質量分析装置であって、
前記絞り手段の開口形状はイオン光軸を中心とする円形であることを特徴とする飛行時間型質量分析装置。 - 請求項1又は2に記載の飛行時間型質量分析装置であって、
前記絞り手段の開口形状はイオン光軸を中心とする長方形状又は楕円形状であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至4のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズを構成する複数の円筒状電極の中で最も入口側に位置する初段の円筒状電極の前縁部の形状は、その頂部にイオン入射開口が形成されたスキマー形状であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至5のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズを構成する複数の円筒状電極の中で最も入口側に位置する初段の円筒状電極の前縁部に形成されたイオン入射開口の形状は円形であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至5のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズを構成する複数の円筒状電極の中で最も入口側に位置する初段の円筒状電極の前縁部に形成されたイオン入射開口の形状は長方形又は楕円形であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至7のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズは、該静電レンズがアフォーカル系となるように駆動されている状態で形成される前記前段の仮想凸レンズの中心と物点との間の距離と、同じ状態で形成される前記後段の仮想凸レンズの中心と像点との間の距離と、が等しい対称配置であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至7のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズは、該静電レンズがアフォーカル系となるように駆動されている状態で形成される前記前段の仮想凸レンズの中心と物点との間の距離と、同じ状態で形成される前記後段の仮想凸レンズの中心と像点との間の距離と、が異なる非対称配置であることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至9のいずれかに記載の飛行時間型質量分析装置であって、
前記電圧印加手段は、前記静電レンズをイオンが通過する前後で該イオンが加速又は減速されるように複数の前記円筒状電極にそれぞれ電圧を印加することを特徴とする飛行時間型質量分析装置。 - 請求項1乃至10のいずれかに記載の飛行時間型質量分析装置であって、
イオンを生成するイオン源から出射されたイオンが直接、前記静電レンズに導入されることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至10のいずれかに記載の飛行時間型質量分析装置であって、
イオンを生成するイオン源と前記静電レンズとの間にイオンガイドを備えることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至10のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズの前段にイオンの解離を促進するコリジョンセルが配置され、該コリジョンセルで生成されたフラグメントイオンが前記静電レンズに導入されることを特徴とする飛行時間型質量分析装置。 - 請求項1乃至10のいずれかに記載の飛行時間型質量分析装置であって、
前記静電レンズの前段にイオンを保持する機能を有するイオントラップが配置され、該イオントラップから出射されたイオンが前記静電レンズに導入されることを特徴とする飛行時間型質量分析装置。
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