Proton transfer reaction mass spectrometer

Abstract

A mass spectrometer includes an ion source configured to generate reagent ions; a drift tube configured to cause sample molecules to react with the reagent ions to generate sample ions, the drift tube comprising two sets of electrodes which are identical in structure and symmetrically distributed in a direction perpendicular to a direction of ion drift, each set of electrodes comprising a plurality of curved cell electrodes which are distributed in a same plane and arranged in the direction of ion drift so that the sample ions are generated and drifted within a region between the two sets of electrodes and focused in the direction perpendicular to the direction of ion drift; a power supply device configured to apply, to each of the cell electrodes, a DC voltage changing in the direction of ion drift; and, a mass analyzer configured to perform mass analysis for the sample ions.

Claims

1. A mass spectrometer, comprising: an ion source configured to generate reagent ions; a drift tube configured to cause sample molecules to react with the reagent ions to generate sample ions, said drift tube comprising two sets of electrodes which are identical in structure and symmetrically distributed in a direction perpendicular to a direction of ion drift, each set of electrodes comprising a plurality of curved cell electrodes which are distributed in a same plane and arranged in the direction of ion drift so that the sample ions are generated and drifted within a region between said two sets of electrodes and focused in the direction perpendicular to the direction of ion drift; a power supply device configured to apply, to each of the cell electrodes, a DC only voltage changing in the direction of ion drift, a periodic focusing DC electric field formed by said DC only voltage being used for ion drift in the direction of ion drift and for ion confinement in the direction perpendicular to the direction of ion drift; and a mass analyzer configured to perform mass analysis for the sample ions.

2. The mass spectrometer according to claim 1, wherein the cell electrodes are ring or arc electrodes, and each set of electrodes comprises several ring or arc electrodes which are distributed in a same plane, have a same center and different radii, and extend in the direction of ion drift.

3. The mass spectrometer according to claim 2, wherein a cross-section of each of the ring or arc electrodes in a direction perpendicular to a ring shape or arc shape is circular or elliptic.

4. The mass spectrometer according to claim 1, wherein a ratio of a distance between two cell electrodes distributed in the direction perpendicular to the direction of ion drift to a width of each cell electrode in the direction of ion drift does not exceed 2, and a ratio of the distance between two cell electrodes distributed in the direction perpendicular to the direction of ion drift to a length of a distance between two adjacent cell electrodes in the direction of ion drift does not exceed 2.

5. The mass spectrometer according to claim 1, wherein the DC voltage applied by the power supply device changes uniformly or non-uniformly in the direction of ion drift, to form a periodic DC focusing electric field in the direction of ion drift.

6. The mass spectrometer according to claim 1, wherein the width of the cell electrodes in the direction of ion drift or a spacing between adjacent cell electrodes in the direction of ion drift changes in the direction of ion drift, to form a periodic DC focusing electric field in the direction of ion drift.

7. The mass spectrometer according to claim 1, wherein the DC voltage is in the form of traveling waves.

8. The mass spectrometer according to claim 1, wherein the cell electrodes are broken line electrodes, and each set of electrodes comprises several broken line electrodes which are distributed in a same plane, have a same axis of symmetry and are arranged in the direction of ion drift.

9. The mass spectrometer according to claim 1, wherein the reagent ions are one of inert gas ions, H.sub.3O.sup.+, NO.sup.+ and O.sub.2.sup.+ or a combination thereof.

10. The mass spectrometer according to claim 1, further comprising an ion selection device which is located in a preceding stage of the drift tube to select one or more of the reagent ions.

11. The mass spectrometer according to claim 1, wherein a pressure in the drift tube ranges from 100 Pa to 400 Pa.

12. The mass spectrometer according to claim 1, wherein the mass analyzer is a quadrupole mass filter, a time-of-flight mass analyzer, an ion trap mass analyzer or a Fourier transform mass analyzer.

13. The mass spectrometer according to claim 1, wherein each set of electrodes is distributed on a same printed circuit board substrate.

14. The mass spectrometer according to claim 1, wherein the reagent ions or the sample molecules are introduced from an annular or arc-shaped inlet into the drift tube for reaction.

Description

BRIEF DESCRIPTION OF DRAWINGS

(1) FIG. 1 shows a structure diagram of a first embodiment of a mass spectrometer according to the present invention;

(2) FIG. 2 shows a three-dimensional structure diagram of a drift tube in the first embodiment of the mass spectrometer according to the present invention;

(3) FIG. 3 shows a schematic diagram of applying a DC voltage to the drift tube in the first embodiment of the mass spectrometer according to the present invention;

(4) FIG. 4 shows a schematic diagram of a DC gradient distribution on the drift tube in a radial direction in the first embodiment of the mass spectrometer according to the present invention;

(5) FIG. 5 shows a schematic diagram of a simulated trajectory in a yz plane during the transmission of ions in the drift tube in the first embodiment of the mass spectrometer according to the present invention;

(6) FIG. 6 shows a schematic diagram of a simulated trajectory in an xy plane during the transmission of ions in the drift tube in the first embodiment of the mass spectrometer according to the present invention;

(7) FIG. 7 shows a schematic diagram of the simulated temperature of ions in the drift tube in the first embodiment of the mass spectrometer according to the present invention;

(8) FIG. 8 shows a structure diagram of a second embodiment of the mass spectrometer according to the present invention;

(9) FIG. 9 shows a three-dimensional structure diagram of a drift tube in the second embodiment of the mass spectrometer according to the present invention;

(10) FIG. 10 shows a planar structure diagram of a third embodiment of the mass spectrometer according to the present invention; and

(11) FIG. 11 shows a three-dimensional structure diagram of the third embodiment of the mass spectrometer according to the present invention.

(12) FIG. 12 shows a mass spectrometer comprising an ion selection device which is located in a preceding stage of the drift tube to select one or more of the reagent ions according to one embodiment of the present invention.

(13) FIG. 13 shows a mass spectrometer where each set of electrodes is distributed on a same printed circuit board substrate according to one embodiment of the present invention.

(14) FIG. 14 shows a mass spectrometer where the reagent ions or the sample molecules are introduced from an annular or arc-shaped inlet into the drift tube for reaction according to one embodiment of the present invention.

DETAILED DESCRIPTION OF THE INVENTION

(15) Implementations of the present invention will be described below by specific embodiments, and other advantages and effects of the present invention can be easily appreciated from the contents disclosed in the description by those skilled in the art.

(16) It is to be noted that, the structure, scale, size and the like shown in the accompanying drawings of the description are merely used for allowing those skilled in the art to understand and read the contents disclosed in the description and not intended to limit the implementable conditions of the present invention, and thus have no any technically substantive meaning. Without influencing the effects and objectives which may be achieved by the present invention, any structural modification, changes in scale, or size adjustments shall fall into the scope defined by the technical contents of the present invention. Meanwhile, terms such as upper, lower, left, right, middle and one used in the description are merely used for clear statement and not intended to limit the implementable scope of the present invention, and any changes or adjustments in relative relations shall be regarded as falling into the implementable scope of the present invention without substantively changing the technical contents.

(17) The mass spectrometer of the present invention includes: an ion source configured to generate reagent ions; a drift tube configured to cause sample molecules to react with the reagent ions to generate sample ions, the drift tube including two sets of electrodes which are identical in structure and symmetrically distributed in a direction perpendicular to a direction of ion drift, each set of electrodes including a plurality of curved cell electrodes which are distributed in a same plane and arranged in the direction of ion drift so that the sample ions are generated and drifted within a region between the two sets of electrodes and focused in the direction perpendicular to the direction of ion drift; a power supply device configured to apply, to each of the cell electrodes, a DC voltage changing in the direction of drift, a DC electric field formed by the DC voltage being used for ion drift; and, a mass analyzer configured to perform mass analysis for the sample ions.

(18) The mass spectrometer of the present invention will be described below in detail with reference to specific embodiments.

Embodiment 1

(19) As shown in FIG. 1, in Embodiment 1, the mass spectrometer of the present invention includes:

(20) an ion source 1 configured to generate reagent ions.

(21) Specifically, the ion source 1 ionizes a reagent gas entering from an inlet a to generate reagent ions. Preferably, the ion source 1 may be a hollow cathode discharge lamp, a radiation source, a microwave plasma source, an electron bombardment ion source or an ion source of other types. The reagent gas may be water vapor, NO, O.sub.2, an inert gas or the like. Accordingly, the reagent ions are preferably one of the following ions or a combination thereof: H.sub.3O.sup.+, NO.sup.+, O.sub.2.sup.+ or inert gas ions, for example, Kr.sup.+ or the like. Preferably, the mass spectrometer further includes an ion selection device 6, which is located in a preceding stage of the drift tube 2 to quickly select one or more of the reagent ions, as shown in FIG. 12.

(22) The drift tube 2 is configured to cause sample molecules to react with the reagent ions to generate sample ions. The drift tube 2 includes two sets of electrodes which are identical in structure and symmetrically distributed in a direction perpendicular to a direction of ion drift. Each set of the electrodes includes a plurality of arc cell electrodes which are distributed in the same plane and arranged in the direction of ion drift so that the sample ions are generated and drifted within a region between the two sets of electrodes and focused in the direction perpendicular to the direction of ion drift.

(23) Preferably, the pressure in the drift tube ranges from 100 Pa to 400 Pa. The drift tube has two functions: firstly, the drift tube functions as a reaction chamber for causing the sample gas to react with the reagent ions to generate sample ions, wherein the sample gas enters the chamber of the drift tube 2 from an inlet b of the chamber where the drift tube is located; and secondly, the drift tube functions as an ion guide device 3 for drifting and transmitting the sample ions to the succeeding stage.

(24) The power supply device (not shown) is configured to apply, to each of the cell electrodes, a DC voltage changing in the direction of ion drift. ADC electric field formed by the DC voltage is used for ion drift. The DC voltage changes uniformly or non-uniformly in the direction of ion drift, to form a periodic DC focusing electric field in the direction of ion drift.

(25) Preferably, the DC voltage is a static DC voltage. However, the DC voltage may be a DC voltage in the form of traveling waves.

(26) The ion guide device 3 is connected to the drift tube 2 to guide the sample ions to a mass analyzer.

(27) The mass analyzer 4 is connected to the ion guide device 3 to perform mass analysis for the sample ions.

(28) Preferably, the mass analyzer may be a quadrupole mass filter, a time-of-flight mass analyzer, an ion trap mass analyzer or a Fourier transform mass analyzer.

(29) A detection device 5 is connected to the mass analyzer 4 to detect the sample ions after being subjected to the mass analysis so as to obtain a mass spectrum.

(30) The structure of the drift tube 2 in this embodiment will be described below in detail. As shown in FIG. 2, the drift tube 2 includes two sets of electrodes which are identical in structure and symmetrically distributed in a direction perpendicular to a direction of ion drift, wherein each set of electrodes includes a plurality of concentric arc electrodes (shown as semi-annular electrodes in the figure) which are distributed in the same plane (i.e., the yz plane), and the arc electrodes (i.e., arc electrodes having an equal radius) in one-to-one correspondence in the two sets of electrodes are distributed in the direction (i.e., x-axis) perpendicular to the direction of ion drift. The region between the two sets of electrodes is a region within which the sample molecules are reacted with the reagent ions to generate sample ions and ion drift is then performed.

(31) In a typical ion drift process, the reagent ions enter the reaction region from a region near the arc electrodes 201 and 202 having a larger radius on the outer side and then react with the sample molecules; the generated sample ions and the remaining reagent ions are focused and transmitted (or drifted) to a region near the arc electrodes 203 and 204 having a smaller radius in the radial direction, until they are gradually focused to the vicinity of the center in the radial direction and eventually introduced into the ion guide device 3 in the succeeding stage from an ion outlet.

(32) Preferably, each set of electrodes can be conventional metal electrodes or can be manufactured by a PCB (Printed Circuit Board) process, so that all electrodes 2 are distributed on the same printed circuit board substrate 7, as shown in FIG. 13. Thus, the manufacturing process is simplified and the manufacturing cost is reduced.

(33) Preferably, the ratio of the distance between two cell electrodes distributed in the direction (i.e., the x direction) perpendicular to the direction of ion drift to the width of each cell electrode in the direction of ion drift (i.e., the radial direction) does not exceed 2, and the ratio of the distance between two cell electrodes distributed in the direction (i.e., the x direction) perpendicular to the direction of ion drift to the length of the distance between two adjacent cell electrodes in the direction of ion drift (i.e., the radial direction) does not exceed 2. By this ratio, periodic focusing or defocusing in the x direction is realized, and the ions are prevented from losing on the electrodes.

(34) In the simplest case, the arc electrodes are identical in both width and spacing in the radial direction, and the power supply device applies a DC voltage changing uniformly in the direction of ion drift to form a periodic DC focusing electric field in the direction of ion drift. As shown in FIG. 3, the resistance of each resistor is equal.

(35) If the cross-section of each of the arc-shaped electrodes in a direction perpendicular to the arc shape is rectangular, high-efficiency ion transmission cannot be realized. Unlike the conventional periodic DC focusing devices, since the periodical change in the DC gradient (i.e., electric field intensity) of the electrodes will be damaged with the reduction of the radius of the arc electrodes, the ions will be overly defocused in the x direction and thus lost on the electrodes.

(36) In order to realize the periodic focusing in the x direction and also realize the focusing or compression of ion beams in the yx plane, the mass spectrometer of the present invention can employ the following solutions.

(37) (1) The cross-section of each of the arc-shaped electrodes in a direction perpendicular to the arc shape is circular or elliptic.

(38) By uniformly applying the DC voltage to the arc electrodes as shown in FIG. 3, a uniform and periodic DC gradient still can be realized, as shown in FIG. 4. In this case, the transmission trajectory of the sample ions is shown in FIGS. 5 and 6. FIG. 5 shows a trajectory of ions in the yz plane, where wider ion beams can be transmitted and focused in the radial direction and then compressed to the vicinity of the center; and, FIG. 6 shows a trajectory of ions in the xy plane, where the ion beams are diffused to a certain extent in the x direction, but the ions are still transmitted at an efficiency of approximately 100%. The reason for the diffusion in the x direction is that there is still a slight over-defocusing effect even though the cross-section of each of the cell electrodes has been modified to be circular or elliptic from rectangular.

(39) (2) A non-uniform DC voltage is applied to each of the cell electrodes.

(40) For example, in order to avoid the over-defocusing of ions, the voltage distribution can be a quadratic curve distribution in the direction of ion drift, that is, the voltage in this direction drops more and more quickly. The increasing voltage gradient will provide an additional ion focusing effect in the x direction.

(41) (3) The width or spacing of the electrodes changes in the direction of ion drift.

(42) For example, in the case where the voltage is uniformly distributed on the cell electrodes, the distance between electrodes can be gradually reduced in the direction of ion drift, so that an additional ion focusing effect is provided.

(43) (4) Very thin (i.e., very narrow) electrodes are used.

(44) In this case, the width of a single electrode in the direction of ion drift and the distance between two electrodes in the x direction do not satisfy the above ratio requirement. However, by adjusting the voltage applied to each electrode, any desired electric field distribution can be obtained. Thus, a periodic focusing electric field can be obtained. However, this solution is complicated and generally requires a special manufacture process, for example, the PCB process.

(45) Therefore, compared with the drift tube in the conventional proton transfer reaction mass spectrometer, the drift tube of the present invention has a very high transmission efficiency. For the conventional DC drift tube, due to the large inner diameter and the small ion outlet, the transmission efficiency generally does not exceed 10%. However, in the present invention, since the drift tube has a periodic ion focusing effect in the x direction and an obvious ion focusing and compression effect in the radial direction, the diffusion of ions can be effectively inhibited, and a transmission efficiency above 80% can be achieved, which is similar to that of the RF focusing technologies like an ion funnel.

(46) Compared with the RF focusing technologies like an ion funnel, the drift tube of the present invention has the following advantages.

(47) (1) Ions will not be heated significantly.

(48) FIG. 7 shows the temperature of ions in the drift tube, which is obtained by computer simulation. During the simulation, the air pressure is 200 Pa, the intensity of the electric field is 60 V/cm, the temperature of ions is equivalently calculated as E/N, i.e., about 120 Td. This is completely consistent with the conventional DC electric field drift tube. Therefore, there will be no water cluster ions, and there will also no fragment ions resulted from obvious cracking. Therefore, an optimal spectrum quality can be realized. However, in the drift tube like an ion funnel, under the same DC electric field intensity, the ions will be significantly heated to about 140 Td even if only a low RF amplitude (e.g., 80V.sub.P-P, 0.5 MHz) is applied.

(49) (2) There is no mass discrimination.

(50) For the ion funnel, low-mass discrimination is likely to occur at the ion outlet due to the RF trapping. However, for the drift tube of the present invention, this problem is overcome, and molecules of a small mass number have a higher transmission efficiency.

(51) (3) Since it is not necessary to apply RF voltage or corresponding RF power supply, the device is relatively simple and the cost is low.

(52) (4) Since the two sets of electrodes in the device are arranged in a planar manner, the device is easily manufactured by a planar process, for example, the PCB process. Therefore, the manufacture difficulty can be reduced greatly.

(53) It is to be noted that, in some particular cases, for example, when it is required to realize further ion trapping in the radial direction (i.e., in a direction perpendicular to the direction of drift), or to heat the ions, or to observe ion fragments, or to remove low-mass ions or the like, the RF voltage can still be applied to the drift tube in the present invention. For example, the RF voltages can be applied to at least part of cell electrodes in each set of electrodes, and the RF voltages on adjacent cell electrodes to which the RF voltages are applied in the direction of drift are equal in amplitude and opposite in phase. In a word, whether an RF voltage is applied or not is not limited in the present invention. Preventing application of an RF voltage is merely to achieve a better spectrum quality in most of analyses.

Embodiment 2

(54) As shown in FIG. 8, a difference between this embodiment and Embodiment 1 lies in that, the arc electrodes are replaced with broken line electrodes, and each set of electrodes includes several broken line electrodes which are distributed in the same plane, have the same axis of symmetry and are arranged in the direction of ion drift. The three-dimensional structure is as shown in FIG. 9. Therefore, in the present invention, the shape of the electrodes of the drift tube is not limited. The electrodes may be curved, and any curved electrodes capable of focusing wide incident ion beams shall fall into the projection scope of the present invention.

Embodiment 3

(55) As shown in FIG. 10, in this embodiment, the cell electrodes are annular electrodes, such that the plane where the two sets of electrodes are located is perpendicular to the direction of the optical axis of the ions in the succeeding stage. With this structure, the instrument becomes more compact, and it is advantageous for the miniaturization of the equipment. Meanwhile, the introduction of the reagent ions and the sample molecules is more flexible. For example, the sample molecules can be introduced along a tangent of the annular electrodes on the outer side, as shown in FIG. 11; or, the sample molecules can be introduced in a direction perpendicular to the plane of the annular electrodes, as shown in FIG. 10; or, the reagent ions and the sample molecules can be distributed around the annular inlet so that they are introduced from the annular inlet, and in this way, the flux of ions can be improved greatly. Of course, the reagent ions and the sample molecules can also be introduced from an annular or arc-shaped inlet b in order to greatly improve the flux of ions, as shown in FIG. 14.

(56) The foregoing embodiments are merely for illustratively describing the principle and effects of the present invention, and not intended to limit the present invention. Those skilled in the art can make modifications or alterations to the embodiments without departing from the spirit and scope of the present invention. Therefore, all equivalent modifications or alterations made by those skilled in the art without departing from the spirit and technical concept of the present invention shall fall into the scope defined by the claims of the present invention.