Mass Spectrometer
20240186134 ยท 2024-06-06
Inventors
Cpc classification
H01J49/42
ELECTRICITY
H01J49/147
ELECTRICITY
International classification
H01J49/42
ELECTRICITY
Abstract
One mode of the mass spectrometer according to the present invention is a mass spectrometer including an ion source configured to ionize a component contained in a sample gas, the ion source (3) including: an ionization chamber (30) having an ion ejection opening (301) and forming a space substantially partitioned from an outside inside the ionization chamber; a thermal electron supply unit (32) configured to supply thermal electrons to an inside of the ionization chamber; a magnetic field forming unit (34, 35) configured to form a magnetic field inside the ionization chamber such that the thermal electrons move helically; and a deflection electric field forming unit (37, 7) configured to form a deflection electric field deflecting ions derived from the component generated in the ionization chamber by a direct or indirect action of the thermal electrons in a direction against a force received from the magnetic field when the ions are moving toward the ion ejection opening.
Claims
1. A mass spectrometer including an ion source configured to ionize a component contained in a sample gas, the ion source comprising: an ionization chamber having an ion ejection opening and forming a space substantially partitioned from an outside inside the ionization chamber; a thermal electron supply unit configured to supply thermal electrons to an inside of the ionization chamber; a magnetic field forming unit configured to form a magnetic field inside the ionization chamber such that the thermal electrons move helically; and a deflection electric field forming unit configured to form a deflection electric field deflecting ions derived from the component generated in the ionization chamber by a direct or indirect action of the thermal electrons in a direction against a force received from the magnetic field when the ions are moving toward the ion ejection opening.
2. The mass spectrometer according to claim 1, wherein the deflection electric field forming unit includes an electrode disposed inside the ionization chamber or as a part of an inner wall of the ionization chamber, and a voltage generator configured to intermittently apply a voltage to the electrode.
3. The mass spectrometer according to claim 1, further comprising a control unit which includes a quadrupole mass filter as a mass separator and which is configured to adjust timing of forming the deflection electric field depending on a mass-to-charge ratio of ions selectively passing through the quadrupole mass filter.
Description
BRIEF DESCRIPTION OF DRAWINGS
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DESCRIPTION OF EMBODIMENTS
[0037] In the mass spectrometer according to the present invention, the ion source performs ionization using thermal electrons, and is specifically, for example, an ion source by the EI method, the CI method, or the NCI method. In addition, a method and a mode of mass separation are not limited to a specific method and mode. In addition, the mass spectrometer may be a mass spectrometer having a region for dissociating ions, such as a collision cell or an ion trap, and capable of performing MS/MS analysis or MS.sup.n analysis (n is an integer of 3 or more).
[0038] Hereinafter, an embodiment of a mass spectrometer according to the present invention will be described with reference to the accompanying drawings.
[0039]
[0040] As illustrated in
[0041] The EI ion source 3 has a substantially rectangular parallelepiped outer shape and includes an ionization chamber 30 made of a conductive material such as metal. An ion ejection opening 301, an electron introduction opening 302, and an electron discharge opening 303 are formed in the side wall, the upper wall, and the lower wall of the ionization chamber 30, respectively. A repeller electrode 31 is disposed inside the ionization chamber 30, a filament 32 outside the electron introduction opening 302, and a trap electrode 33 outside the electron discharge opening 303. In addition, a pair of magnets 34 and 35 is disposed above and below the filament 32 and the trap electrode 33 so as to sandwich the filament and the trap electrode, and two pieces of extraction electrodes 36A and 36B (collectively referred to as reference numeral 36) in which an ion passing opening is formed are disposed outside the ion ejection opening 301. Furthermore, a deflection electrode 37 is disposed inside the ionization chamber 30, and a sample gas introduction tube 304 is connected to a side wall of the ionization chamber 30.
[0042] The ionization chamber 30 is grounded and has a potential of 0 V. A predetermined DC voltage Vd is applied from the deflection voltage generator 7 to the deflection electrode 37. The deflection voltage generator 7 is controlled by a control unit 9 together with the quadrupole voltage generator 8 that applies a voltage to each electrode of the quadrupole mass filter 5. Although not illustrated in
[0043] Next, an operation for a mass spectrometric analysis performed in the mass spectrometer according to the present embodiment is described with reference to
[0044] The sample gas is introduced into the ionization chamber 30 from, for example, a direct sample introduction device through the sample gas introduction tube 304. An electric current is supplied to the filament 32. The filament 32 is thereby heated and generates thermal electrons. A predetermined potential difference is formed between the filament 32 and the trap electrode 33 by voltages respectively applied to the filament and the trap electrode, and thermal electrons are accelerated by the potential difference and travel toward the trap electrode 33. That is, as illustrated in
[0045] Sample molecules contained in the sample gas are ionized by being brought into contact with thermal electrons. The extrusion electric field formed in the ionization chamber 30 by the potential difference between the repeller electrode 31 and the inner wall of the ionization chamber 30 has an action of pushing the ions generated as described above substantially in the Z-axis direction, that is, in the direction toward the ion ejection opening 301. Whereas, the extraction electrode 36 is supplied with a direct voltage having an opposite polarity to the ions. The extracting electric field created by this voltage penetrates into the ionization chamber 30 through the ion ejection opening 301. This extracting electric field has the effect of forcing the ions to move toward the ion ejection opening 301. The ions generated in the ionization chamber 30 are extracted to the outside through the ion ejection opening 301 by the action of both the extrusion electric field and the extraction electric field, and are introduced into the ion transport optical system 4.
[0046] Within the ion transport optical system 4, the ions are temporarily converged into an area near the ion optical axis C and sent to the quadrupole mass filter 5. A predetermined voltage obtained by superimposing a radio-frequency voltage (RF voltage) on a DC voltage is applied from the quadrupole voltage generator 8 to four pieces of the rod electrodes constituting the quadrupole mass filter 5, and only ions having a specific mass-to-charge ratio corresponding to the voltage selectively pass through the quadrupole mass filter 5. The ion detector 6 produces a detection signal corresponding to the amount of ions which have reached the same detector. Accordingly, for example, by controlling the applied voltage so that the mass-to-charge ratio of the ion which is allowed to pass through the quadrupole mass filter 5 continuously varies within a predetermined range, a set of mass spectrum data which show the ionic intensity over the predetermined range of mass-to-charge ratios can be acquired.
[0047] Next, a characteristic configuration and operation of the EI ion source 3 will be described with reference to
[0048] As described above, a magnetic field is formed inside the ionization chamber 30. The magnetic flux lines in the magnetic field are oriented in a direction orthogonal to the paper surface of
[0049]
[0050] As illustrated in
[0051] As is clear from comparison between
[0052] In the mass spectrometer of the present embodiment, as illustrated in
[0053]
[0054] In the mass spectrometer of the present embodiment, generally analysis in either a scan mode or a selected ion monitoring (SIM) mode is performed.
[0055] The scan range of the mass scan is, for example, m/z 1 to m/z 1000, and in the example illustrated in
[0056] Thus, when performing analysis in the scan mode, it is possible to efficiently extract ions generated by the EI ion source 3 from the ionization chamber 30 and analyze by the quadrupole mass filter 5 for ions having any mass-to-charge ratio from a low mass-to-charge ratio to a high mass-to-charge ratio. As a result, high analysis sensitivity for any ion can be achieved.
[0057] In the case of the SIM mode, the mass-to-charge ratio of the ions to be measured is determined, and thus using this mass-to-charge ratio, it may be determined whether the deflection voltage Vd is applied to the deflection electrode 37.
[0058] In addition, the degree of bending of the trajectory due to the magnetic field varies depending on the mass-to-charge ratio, and thus the degree of improvement of the analysis sensitivity can be increased by switching the value of the deflection voltage Vd not only in binary but in multiple stages.
[0059] The mass spectrometer of the above embodiment uses a quadrupole mass filter as a mass separator, and measures only ions having a certain specific mass-to-charge ratio at a certain time point, so that the above-described control can be performed. Whereas, in a mass spectrometer using, for example, a fan-shaped magnetic field-type mass separator, a quadrature acceleration time-of-flight mass separator, or the like as a mass separator, ions that have entered the mass separator at substantially the same time are separated according to the mass-to-charge ratio, and thus, it is not possible to adopt the control as described above. Therefore, in such a mass spectrometer, the following control may be performed.
[0060]
[0061]
[0062] As illustrated in
[0063] From these results, it can be concluded that if the period for forming the deflection electric field is 2 us, light ions of at least m/z 2 to 4 can reliably pass through the ion passing opening of the extraction electrode 36A, whereas heavy ions of m/z 100 or more can pass through the ion passing opening of the extraction electrode 36A with a small loss substantially without being affected by the deflection electric field.
[0064] Therefore, in a case where it is desired to send ions having a wide mass-to-charge ratio generated in the ionization chamber 30 substantially simultaneously to the subsequent stage, the control unit 9 may control the deflection voltage generator 7 so that the deflection voltage is intermittently applied to the deflection electrode 37 as illustrated in
[0065] Whereas, tb may be appropriately determined according to the upper limit value of the mass-to-charge ratio range to be measured. For example, if the upper limit value is m/z 500, it can be found from
[0066] In the mass spectrometer of the above embodiment, the deflection electrode 37 for forming a deflection electric field in the ionization chamber 30 is disposed in the ionization chamber 30, but in general, the ionization chamber is very small, and it may be difficult to add a new electrode inside the ionization chamber 30. In this case, a configuration as illustrated in
[0067] In the example illustrated in
[0068] In the example illustrated in
[0069] The previously described embodiment and its modifications are mere examples of the present invention. Any change, modification, or addition appropriately made within the spirit of the present invention will evidently fall within the scope of the claims of the present application.
[0070] For example, the mass spectrometer of the above embodiment uses the EI ion source, but may be an ion source that performs ionization using thermal electrons and uses a magnetic field for convergence of thermal electrons. Therefore, the present invention can also be applied to, for example, a mass spectrometer using a CI ion source or an NCI ion source.
[0071] In addition, as described above, the configuration of the device except for the ion source is not limited to that of the previously described embodiment and may be appropriately changed. Therefore, it is reasonable that the mass spectrometer according to the present invention can be applied not only to a single-type quadrupole mass spectrometer but also to various types of mass spectrometers such as a time-of-flight mass spectrometer, an ion trap mass spectrometer, a triple quadrupole mass spectrometer, a fan-shaped magnetic field mass spectrometer, and an ion movement-mass spectrometer.
[Various Modes]
[0072] A person skilled in the art can understand that the previously described illustrative embodiment is a specific example of the following modes of the present invention.
[0073] (Clause 1) One mode of the mass spectrometer according to the present invention is a mass spectrometer including an ion source configured to ionize a component contained in a sample gas, the ion source including: [0074] an ionization chamber having an ion ejection opening and forming a space substantially partitioned from an outside inside the ionization chamber; [0075] a thermal electron supply unit configured to supply thermal electrons to an inside of the ionization chamber; [0076] a magnetic field forming unit configured to form a magnetic field inside the ionization chamber such that the thermal electrons move helically; and [0077] a deflection electric field forming unit configured to form a deflection electric field deflecting ions derived from the component generated in the ionization chamber by a direct or indirect action of the thermal electrons in a direction against a force received from the magnetic field when the ions are moving toward the ion ejection opening.
[0078] In the ion source of the mass spectrometer according to Clause 1, the thermal electrons supplied into the ionization chamber by the thermal electron supply unit travel while helically swirling by the action of the magnetic field formed by the magnetic field forming unit. As described above, the magnetic field has an action of suppressing the spread of the thermal electron flow, but ions having a low mass-to-charge ratio are also affected by the magnetic field, and the ion trajectory is bent when the ions travel toward the ion ejection opening.
[0079] In the mass spectrometer according to Clause 1, the bending of the trajectory generated when the ions generated in the ionization chamber receive the force from the magnetic field is corrected by the action of the electric field formed by the deflection electric field forming unit. With this configuration, it is possible to suppress loss when ions generated in the ionization chamber are extracted from the ionization chamber to the outside, and to improve ion extraction efficiency. As a result, a larger amount of ions can be subjected to mass spectrometry, and the analysis sensitivity can be improved.
[0080] In order to improve the analysis sensitivity of light ions whose trajectory is easily bent due to the influence of the magnetic field, a deflection electric field having a predetermined electric field intensity may be continuously formed, but in this case, the trajectory of heavy ions that are hardly affected by the magnetic field are likely to be bent due to the influence of the deflection electric field, and an ion loss may occur.
[0081] (Clause 2) Therefore, in the mass spectrometer according to Clause 1, the deflection electric field forming unit may include an electrode disposed inside the ionization chamber or as a part of an inner wall of the ionization chamber, and a voltage generator configured to intermittently apply a voltage to the electrode.
[0082] With the mass spectrometer described in Clause 2, light ions are efficiently sent to the subsequent stage during a period in which the deflection electric field is formed, whereas heavy ions are efficiently sent to the subsequent stage during a period in which the deflection electric field is not formed. As a result, it is possible to supply entire ions including light ions to heavy ions in a well-balanced manner and to improve the analysis sensitivity for ions having a wide mass-to-charge ratio.
[0083] (Clause 3) In addition, the mass spectrometer according to Clause 1 may further include a control unit which includes a quadrupole mass filter as a mass separator and which is configured to adjust timing of forming the deflection electric field depending on a mass-to-charge ratio of ions selectively passing through the quadrupole mass filter.
[0084] For example, when the mass-to-charge ratio of ions passing through the quadrupole mass filter is scanned in order to perform the analysis of the scan mode, a deflection electric field may be formed when light ions are emitted from the ion source in accordance with the timing at which the light ions pass through the quadrupole mass filter. That is, the scanning of the voltage applied to the electrode constituting the quadrupole mass filter is synchronized with the timing of forming the deflection electric field in the ionization chamber. Thus, when performing scan mode analysis, it is possible to perform analysis with high sensitivity for any ions from ions with a low mass-to-charge ratio to ions with a high mass-to-charge ratio.
[0085] Whereas, in a case where analysis of ions having a specific mass-to-charge ratio is performed for a certain period of time as in the SIM mode, whether a deflection electric field is formed or not may be switched according to the mass-to-charge ratio.
REFERENCE SIGNS LIST
[0086] 1 . . . Chamber [0087] 3 . . . EI Ion Source [0088] 30 . . . Ionization Chamber [0089] 301 . . . Ion Ejection Opening [0090] 302 . . . Electron Introduction Opening [0091] 303 . . . Electron Discharge Opening [0092] 304 . . . Sample Gas Introduction Tube [0093] 305 . . . Insulating Member [0094] 30A, 30B . . . Partial Ionization Chamber [0095] 31 . . . Repeller Electrode [0096] 32 . . . Filament [0097] 33 . . . Trap Electrode [0098] 34, 35 . . . Magnet [0099] 36, 36A . . . Extraction Electrode [0100] 37, 37B . . . Deflection Electrode [0101] 4 . . . Ion Transport Optical System [0102] 5 . . . Quadrupole Mass Filter [0103] 6 . . . Ion Detector [0104] 7 . . . Deflection Voltage Generator [0105] 8 . . . Quadrupole Voltage Generator [0106] 9 . . . Control Unit