Ionization device and mass spectrometer
阅读说明:本技术 离子化装置和质谱分析装置 (Ionization device and mass spectrometer ) 是由 西口克 于 2018-02-06 设计创作,主要内容包括:一种离子化装置(1)以及具备该离子化装置(1)的质谱分析装置(60),其中,该离子化装置(1)包括:离子化室(10);试样气体导入口(14),其设于离子化室(10),用于导入试样气体;电子束释放部(11),其用于朝向离子化室(10)释放电子束;电子束通过口(10a、10b),其形成于离子化室(10)的壁面的、供从电子束释放部(11)释放的电子束通过的路径上,该电子束通过口的在该路径的方向上的长度比与该方向正交的截面的宽度长;以及离子出口(10c),其设于离子化室(10),用于将通过照射电子束而生成的试样气体的离子释放。(An ionization device (1) and a mass spectrometer (60) provided with the ionization device (1), wherein the ionization device (1) comprises: an ionization chamber (10); a sample gas inlet (14) provided in the ionization chamber (10) and used for introducing a sample gas; an electron beam discharge section (11) for discharging an electron beam toward the ionization chamber (10); electron beam passage openings (10a, 10b) formed in a path of a wall surface of the ionization chamber (10) through which the electron beam emitted from the electron beam emitting section (11) passes, the length of the electron beam passage opening in the direction of the path being longer than the width of a cross section orthogonal to the direction; and an ion outlet (10c) provided in the ionization chamber (10) and configured to discharge ions of the sample gas generated by the irradiation of the electron beam.)
1. An ionization apparatus, comprising:
a) an ionization chamber;
b) a sample gas inlet provided in the ionization chamber and configured to introduce a sample gas;
c) an electron beam discharge section that discharges an electron beam toward the ionization chamber;
d) an electron beam passage opening formed in a path of the wall surface of the ionization chamber through which the electron beam emitted from the electron beam emitting portion passes, the length of the electron beam passage opening in a direction of the path being longer than a width of a cross section orthogonal to the direction; and
e) and an ion outlet provided in the ionization chamber, for releasing ions of the sample gas generated by irradiation of the electron beam.
2. The ionization apparatus according to claim 1,
the two electron beam passage ports are formed symmetrically with respect to the center of the internal space of the ionization chamber.
3. The ionization apparatus according to claim 1,
a repeller electrode for forming a pushing electric field that pushes ions in a direction toward the ion outlet is also included inside the ionization chamber.
4. A mass spectrometry device characterized in that,
the mass spectrometry device comprises:
the ionization apparatus of claim 1;
a mass separation section for separating ions generated by the ionization device according to a predetermined mass-to-charge ratio; and
a detector for detecting ions exited by the ion separation section.
5. A mass spectrometry apparatus, comprising:
the ionization apparatus of claim 1;
a quadrupole mass filter for separating ions generated by the ionization device according to mass-to-charge ratio; and
a detector for detecting ions separated by the quadrupole mass filter.
6. A mass spectrometry apparatus, comprising:
the ionization apparatus of claim 1;
a front-end quadrupole mass filter for separating ions generated by the ionization device according to mass-to-charge ratio;
an ion dissociation unit for dissociating the ions selected by the front-stage quadrupole mass filter;
a rear stage quadrupole mass filter for separating product ions generated by dissociation in the ion dissociation section according to a mass-to-charge ratio; and
a detector for detecting ions separated by the posterior quadrupole mass filter.
7. A mass spectrometry apparatus, comprising:
the ionization apparatus of claim 1;
a time-of-flight mass separation unit of an orthogonal acceleration system for separating ions generated by the ionization device according to a mass-to-charge ratio; and
a detector for detecting ions exiting from the time-of-flight mass separation section.
8. A mass spectrometry apparatus, comprising:
the ionization apparatus of claim 1;
a quadrupole mass filter for separating ions generated by the ionization device according to mass-to-charge ratio;
an ion dissociation unit for dissociating the ions selected by the quadrupole mass filter;
a time-of-flight mass separation unit of an orthogonal acceleration system for separating product ions generated by dissociation in the ion dissociation unit according to a mass-to-charge ratio; and
a detector for detecting ions exiting from the time-of-flight mass separation section.
9. A mass spectrometry apparatus, comprising:
the ionization apparatus of claim 1;
a double-focusing type mass separation section that separates ions generated by the ionization device according to a mass-to-charge ratio by a sector magnetic field and a sector electric field; and
a detector for detecting ions exited by the dual focusing mass separation section.
Technical Field
The present invention relates to an Ionization apparatus for ionizing a sample gas, and more particularly, to an Ionization apparatus for ionizing a sample gas by an Electron Ionization (EI) method, a Chemical Ionization (CI) method, or a Negative Chemical Ionization (NCI) method. The present invention also relates to a mass spectrometer equipped with such an ionization device.
Background
In a mass spectrometer that ionizes a sample gas and analyzes the sample gas, such as a gas chromatograph-mass spectrometer (GC-MS), an ionizer that ionizes the sample gas by an electron ionization method, a chemical ionization method, or a negative chemical ionization method is used. In the electron ionization method, a sample gas is introduced into an ionization chamber and an electron beam is irradiated to ionize molecules in the sample gas (for example, patent document 1). In the chemical ionization method, a reactive gas is introduced into an ionization chamber together with a sample gas, and molecules in the reactive gas are ionized by irradiating the chamber with an electron beam, and the molecules in the sample gas are ionized by reacting the ions with the molecules in the sample gas. Negative chemical ionization has various ionization mechanisms, such as the generation of negative ions by the trapping of thermal electrons by molecules in the sample gas. The generated ions are transported to a mass separation unit such as a quadrupole mass filter, separated according to the mass-to-charge ratio, and detected.
Fig. 1 shows a schematic configuration of a conventional ionization apparatus 100 for ionizing a sample gas by an electron ionization method. In the ionization apparatus 100, a sample gas is introduced into an ionization chamber 110 disposed in a vacuum-exhausted chamber (not shown) and ionized. The ionization chamber 110 has a box shape formed by combining plate members. Two filaments 111 and 112 are disposed outside the ionization chamber 110 with the ionization chamber 110 interposed therebetween. In use, a predetermined current is supplied to one filament 111 to generate thermionic electrons, which are released toward the other filament 112. Electron beam passing openings 110a and 110b are formed in an electron beam path connecting the filaments 111 and 112 on the wall surface of the ionization chamber 110. An ion outlet 110c is formed in the other wall surface of the ionization chamber 110, and an ion transport optical system 120 for converging ions extracted from the ionization chamber 110 and transporting the ions to a mass separation unit or the like is disposed outside the ion outlet. A repeller electrode 113 is disposed in the ionization chamber 110, and when a dc voltage having the same polarity as that of the ions to be measured is applied to the repeller electrode 113, an electric field is formed in the ionization chamber 110 so as to push the ions toward the ion outlet 110c, thereby releasing the ions from the ionization chamber 110.
Disclosure of Invention
Problems to be solved by the invention
In a mass spectrometer, it is required to improve measurement sensitivity. Since the electron ionization method is a method of generating ions by irradiating molecules in the sample gas present in the ionization chamber 110 with an electron beam, it is conceivable to increase the number density of molecules in the sample gas in the ionization chamber 110 to increase the amount of ions generated in order to increase the measurement sensitivity.
Since the sample gas introduced into the ionization chamber 110 flows out from the electron beam passage openings 110a and 110b or the ion outlet 110c, the number density of molecules in the ionization chamber 110 can be increased by reducing the size of the openings. However, since the incidence amount of the electron beam to the ionization chamber 110 decreases when the electron beam passage openings 110a and 110b are narrowed, the amount of ions generated does not increase as a result even if the number density of molecules of the sample gas in the ionization chamber 110 increases. Further, when the ion outlet 110c is narrowed, the amount of the sample gas flowing out of the ionization chamber 110 is reduced, the number density of molecules in the ionization chamber 110 is increased, and the amount of ions generated is increased, but the amount of ions released from the ionization chamber 110 is reduced, and thus the measurement sensitivity is not improved. That is, even if the electron beam passage openings 110a and 110b or the ion exit 110c are narrowed to increase the number density of molecules in the ionization chamber 110, it is difficult to increase the measurement sensitivity.
Here, the case of using an ionization apparatus using an electron ionization method is described as an example, but the same applies to an ionization apparatus using a chemical ionization method for ionizing a sample gas by using an electron beam as in the electron ionization method, or a negative chemical ionization method.
An object of the present invention is to provide an ionization device capable of improving the measurement sensitivity of ions generated from a sample gas. Further, a mass spectrometer provided with such an ionization device is provided.
Means for solving the problems
An ionization device according to the present invention, which has been made to solve the above problems, includes:
a) an ionization chamber;
b) a sample gas inlet provided in the ionization chamber and configured to introduce a sample gas;
c) an electron beam discharge section that discharges an electron beam toward the ionization chamber;
d) an electron beam passage opening formed in a path of the wall surface of the ionization chamber through which the electron beam emitted from the electron beam emitting portion passes, the length of the electron beam passage opening in a direction of the path being longer than a width of a cross section orthogonal to the direction; and
e) and an ion outlet provided in the ionization chamber, for releasing ions of the sample gas generated by irradiation of the electron beam.
The cross-sectional shape of the electron beam passage opening is, for example, circular, and in this case, the width is defined by a diameter. However, in the present invention, the electron beam passage opening is not limited to a circular shape, and may be an elliptical shape or a polygonal shape. For example, in the case where the electron beam emitting portion has a filament that is long in a direction orthogonal to the emission direction of the electron beam, it is desirable to form the electron beam passage opening in a rectangular or elliptical shape that is long in the direction because the electron beam having a long cross section in the direction is generated. As will be described later, based on the technical idea of reducing the molecular flow conductivity of the electron beam passage opening, when the cross section of the electron beam passage opening is a shape other than a circle (an ellipse, a rectangle, or the like) as described above, the width is defined by the length corresponding to the diameter of a circle having the same cross section.
The ionization device of the present invention has the following features: an electron beam passage opening provided in an ionization chamber of the ionization apparatus has a length in a direction in which an electron beam passes, which is longer than a width of a cross section orthogonal to the direction. An ionization chamber used in a conventional ionization apparatus is formed by combining a plate-shaped member having a thickness of, for example, 1mm or less, and an electron beam passage opening formed in the plate-shaped member having a diameter of, for example, about 3 mm. That is, in the conventional ionization apparatus, the length of the electron beam passage opening formed in the ionization chamber in the direction in which the electron beam passes is shorter than the width of the cross section orthogonal to the direction. In contrast, in the ionization apparatus of the present invention, for example, a plate-shaped member having a thickness of 5mm is used, and an electron beam passage opening having a diameter of about 3mm is formed in the same manner as in the conventional apparatus. This reduces the molecular flow conductivity of the electron beam passage opening as compared with conventional ionization apparatuses, and prevents the sample gas from flowing out of the ionization chamber. As a result, the number density of molecules of the sample gas in the ionization chamber becomes high. In the ionization apparatus of the present invention, the width of the electron beam passage opening formed in the ionization chamber may be the same as that of the conventional one, and the amount of incidence of the electron beam into the ionization chamber is not reduced, so that the amount of ions generated is increased. Further, since the ion outlet is also required to be the same as in the conventional case, the amount of ions released from the ionization chamber is not reduced. Thus, the measurement sensitivity can be improved.
In the ionization apparatus of the present invention, it is preferable that the two electron beam passage openings are formed symmetrically with respect to a center of the internal space of the ionization chamber. In this way, for example, by arranging two filaments, when one of the filaments serving as the electron beam emitting portion is off, the other filament can be operated as the electron beam emitting portion, and the two electron beam passing ports are arranged at equivalent positions, so that even if the filaments are switched, an equivalent structure can be maintained.
The ionization apparatus of the present invention can be suitably used as an ionization section of a mass spectrometer.
ADVANTAGEOUS EFFECTS OF INVENTION
By using the ionization device of the present invention or the mass spectrometer equipped with the ionization device, the measurement sensitivity of ions generated from the sample gas can be improved.
Drawings
Fig. 1 is a schematic configuration diagram of a conventional ionization apparatus.
Fig. 2 is a schematic configuration diagram of an ionization apparatus according to an embodiment of the present invention.
Fig. 3 is a schematic configuration diagram of a quadrupole mass spectrometer according to an embodiment of the present invention.
Fig. 4 is a simulation result of the number density of molecules in the ionization chamber of the ionization apparatus of the present embodiment.
Fig. 5 is a mass chromatogram obtained using a gas chromatograph-mass spectrometer in which the quadrupole mass spectrometer of the present example and a gas chromatograph are combined.
Fig. 6 is an overall configuration diagram of a triple quadrupole mass spectrometer according to another embodiment of the mass spectrometer of the present invention.
Fig. 7 is an overall configuration diagram of a time-of-flight mass spectrometer of an orthogonal acceleration system as still another embodiment of the mass spectrometer of the present invention.
Fig. 8 is an overall configuration diagram of a quadrupole-time-of-flight mass spectrometer according to still another embodiment of the mass spectrometer of the present invention.
Fig. 9 is an overall configuration diagram of an electric-field magnetic-field double-focusing mass spectrometer according to still another embodiment of the mass spectrometer of the present invention.
Detailed Description
An embodiment of an ionization apparatus according to the present invention and a quadrupole mass spectrometer as an embodiment of a mass spectrometer including the ionization apparatus according to the embodiment will be described below with reference to the drawings. Fig. 2 is a main part configuration diagram of an
The
In the
The quadrupole mass spectrometer 60 of the present embodiment is a so-called single quadrupole mass spectrometer, and includes the
In the
The ion transport
As described above, the
In a conventional ionization apparatus, in order to reduce the weight of the apparatus, an ionization chamber is configured by combining thin plate-shaped members (for example, having a thickness of 0.5mm), and two openings having a diameter of, for example, about 3mm are formed in a path of an electron beam, and these openings are used as electron beam passage openings.
In contrast, in the
In the case where the
In addition, considering only the reduction of the conductivity, the method of reducing the inner diameters of the electron beam passage openings is more efficient than the method of lengthening the electron beam passage openings. However, since the incidence amount of the electron beam to the ionization chamber is reduced by reducing the inner diameter of the electron beam passage opening, the amount of ions generated does not increase even if the number density of molecules of the sample gas in the ionization chamber is increased.
Alternatively, it is also considered to increase the number density of molecules in the ionization chamber by increasing the conductivity of the ion outlet or by decreasing the inner diameter. However, in this case, the amount of ions released from the ionization chamber also decreases, and therefore the measurement sensitivity does not increase.
In the
In the
Next, a simulation for confirming the effect obtained by using the ionization device of the present embodiment will be described. In this simulation, the number density of molecules on the path (y-axis) of the electron beam in the ionization chamber was determined for each of the ionization apparatus of this example and the conventional ionization apparatus (comparative example). As described above, since the ionization apparatus of the present embodiment is used in a vacuum environment, the sample gas flows as a molecular stream, and thus the direct simulation Monte Carlo (DSMC: direct simulation Monte Carlo) method is used as a simulation (for example, patent document 2).
In both the ionization device of the present embodiment and the ionization device of the comparative example, the sectional shapes of the electron beam entrance port and the electron beam exit port were set to be rectangles of 2mm × 4mm, and their lengths were set to be 5mm in the present embodiment and 0.5mm in the comparative example. Further, the sample gas flow is introduced from the center of the one side surface parallel to the path of the electron beam, and the point of intersection of the path of the electron beam and the introduction direction of the sample gas flow is the origin.
FIG. 4 shows the results of the simulation, and it is found that the molecular number density of the sample gas in the path of the electron beam in the comparative example is about 2.0 × 1020Per m3In contrast, in the present example, the molecular number density of the sample gas in the path of the electron beam was increased to about 2.5 × 1020Per m3。
In addition, the experimental results for confirming the effects obtained by using the ionization device of the present example will be described. In this experiment, the same standard sample was introduced into each gas chromatograph-mass spectrometer obtained by combining a gas chromatograph in the front stage of each of the quadrupole mass spectrometer having the configuration described with reference to fig. 3 and the quadrupole mass spectrometer having the conventional ionizer (comparative example), and Selective Ion Monitoring (SIM) was performed on a sample component contained in the standard sample and having a retention time of about 3.95 min.
The mass chromatogram obtained from the above experiment is shown in fig. 5. It was found that the detection intensity of ions (arbitrary unit common to the present example and the comparative example) in the mass chromatogram was about 14,000 in the comparative example, whereas the detection intensity of ions was large, about 21,000 in the present example, and the measurement sensitivity of ions was improved by about 5 times compared to the conventional one.
The above embodiments are examples, and can be modified as appropriate according to the spirit of the present invention.
In the above embodiment, the two
In the above-described embodiments, the case where the sample gas is ionized by the electron ionization method has been described as an example, but the same configuration as described above is also suitably used for an ionization apparatus using a chemical ionization method for ionizing the sample gas by using an electron beam as in the electron ionization method, or a negative chemical ionization method.
In the above-described embodiment, the quadrupole mass spectrometer 60 was described, but the
Fig. 6 is an overall configuration diagram of a so-called triple
In the triple
In addition to the MS scan measurement and the SIM measurement, the triple
Fig. 7 is an overall configuration diagram of a time-of-
In this time-of-flight mass spectrometer, ions generated in the
Fig. 8 is a diagram showing the entire configuration of a quadrupole-time-of-flight (q-TOF) mass spectrometer 63. The quadrupole-time-of-flight mass spectrometer 63 includes the
In the quadrupole-time-of-flight mass spectrometer 63, ions generated in the
Fig. 9 is an overall configuration diagram of the magnetic field/electric field double focusing
In the magnetic field-electric field double focusing
Description of the reference numerals
1 … ionization device; 10 … ionization chamber; 10a, 10b … electron beam passing port; 10c … ion outlet; 11. 12 … filament; 13 … repeller electrodes; 14 … sample gas inlet; 15 … voltage applying part; 20 … ion transport optics; 30 … quadrupole mass filter; 31 … front-stage quadrupole mass filter; a 32 … multipole ion guide; 33 … collision cell; 34 … rear segment quadrupole mass filter; 35 … orthogonal accelerator; 40-44 … ion detector; 50-54 … chambers; a 60 … quadrupole mass spectrometer; 61 … triple quadrupole mass spectrometer; 62 … time-of-flight mass spectrometry; 63 … quadrupole-time-of-flight mass spectrometer; 64 … magnetic field and electric field double focusing mass spectrometer; 71 … flight space; 72 … reflector; 81 … electric field sector; 82 … magnetic field sector.
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