Patent Application
20110012017
The present invention relates to a mass spectrometer, and more specifically to an ion optical system for transporting ions to subsequent stages in the mass spectrometer.
In mass spectrometers, an ion optical system, which is also referred to as an ion lens or ion guide, is used to converge ions supplied from the previous stage, accelerate them in some cases, and send them to a mass analyzer (e.g. a quadrupole mass filter) in the next stage. Some conventional ion optical systems use multipole rod configurations, such as a quadrupole or octapole system. In the case of a quadrupole mass filter, which is often used as a mass analyzer for separating ions according to their mass, a set of short pre-rod electrodes may be additionally provided before the main quadrupole rod electrodes to smoothly introduce ions into the main rod electrodes. Furthermore, a set of short post-rod electrodes may also be provided after the main quadrupole rod electrodes to prevent the movement of ions from being disturbed due to a disturbance of the electric field at the rear end of the quadrupole rod electrodes. These pre-rod and post-rod electrodes are also a type of ion optical systems.
In the multipole rod ion optical system with four or more poles, the profile of the radio-frequency electric field formed within the space surrounded by the rod electrodes changes depending on the number of poles. This change is accompanied by some changes in the ion optical characteristics, such as the ion beam convergence, ion transmission efficiency, ion acceptance, ion-storing capacity and mass-separating capability. In general, using a smaller number of poles improves the beam convergence and mass-selecting capability due to the cooling effect caused by a collision with neutral molecules; increasing the number of poles lowers the beam convergence and mass-selecting capability while improving the transmission efficiency and acceptance of the ions.
Patent Documents 1, 2 and other documents disclose an ion optical system using virtual rod electrodes.
However, in the case of the virtual rod electrodes 731-734, it is possible to apply a different voltage to each of the plate electrodes forming one virtual rod electrode. Therefore, for example, a DC voltage that increases in a stepwise manner along the moving direction of the ions is superimposed on the radio-frequency voltage. The DC electric field created by this DC voltage has the effect of accelerating or decelerating the ions passing through the space surrounded by the virtual rod electrodes 731-734. Thus, the acceleration or deceleration of the ions can be easily performed. Furthermore, in the present configuration, the plate electrodes forming one virtual rod electrode can be arranged so that they come closer to the ion beam axis C with the movement of the ions. In this configuration, the space within which the ions can oscillate becomes smaller with the movement of the ions. Consequently, the ions are converged closer to the ion beam axis C so that, for example, they can be efficiently guided through a small hole formed at the tip of a skimmer and transported to the next stage.
Patent Document 1: Japanese Unexamined Patent Application Publication No. 2000-149865
Patent Document 2: Japanese Unexamined Patent Application Publication No. 2001-351563
As already explained, the ion optical characteristics of the conventional multipole rod ion optical system vary depending on the number of poles. Therefore, the system is normally designed so that the number of poles is appropriately selected according to the atmospheric conditions (e.g. gas pressure) under which the ion optical system will be used, the relation of the ion optical system with other ion-optical elements provided before or after itself and other factors, and the necessary parameters (e.g. the diameter and length of the rod electrodes) are determined for the selected number of poles. However, the conventional ion optical system has a limited range of choice for the parameters and does not always allow the use of an ion optical system having optimal ion optical characteristics for the intended application. Therefore, in some cases, it is difficult to improve the detection sensitivity or accuracy of the system.
By contrast, in the conventional virtual-rod ion optical system, each virtual rod electrode is composed of a plurality of plate electrodes and their geometrical arrangement can be chosen with high degrees of freedom, so that the plate electrodes can be arranged in a special manner to improve the convergence of the ions, as in the previously described case. Furthermore, the acceleration or deceleration of ions can be achieved by applying a DC voltage in a stepwise manner. However, composing one virtual rod electrode from many plate electrodes inevitably increases the number of parts, and the task of assembling and adjusting those plate electrodes is difficult since they must be accurately arranged. Therefore, it is difficult to construct a virtual-rod electrode system with eight or more poles.
In recent years, a higher sensitivity, higher accuracy, higher throughput, and other improvements in a mass spectrometer have been required in order to deal with the growing diversity and complexity of the kind of substances to be analyzed, the demand for a prompt analysis, and other requests. To meet such demands, it is also necessary to improve the performance of the ion optical system. However, improving the system performance on the basis of the conventional multipole rod configuration has practical limitations due to the aforementioned reasons. In the case of the virtual-rod multipole configuration, improving the ion transmission efficiency and other ion optical characteristics by increasing the number of poles is rather impractical mainly because of its high cost.
The present invention has been developed to solve the aforementioned problems, and its main objective is to provide a mass spectrometer whose detection sensitivity and analysis accuracy are enhanced by improving the performance an ion optical system which converges ions coming from the previous stage, accelerates or decelerates these ions in some cases, and sends them to the next stage.
Another objective of the present invention is to provide a mass spectrometer having an ion optical system capable of easily and inexpensively realizing the required properties, such as the ion transmission efficiency, ion acceptance and mass-selecting capability, according to the atmospheric gas pressure or other usage conditions.
No extensive analysis has previously been made on the radio-frequency electric field created in the aforementioned type of virtual multipole rod ion optical system; it has been taken for granted that this system should create a radio-frequency electric field similar to the one created by a normal multipole rod ion optical system with the same number of poles. The present inventor has conducted an analysis focused on the radio-frequency electric field created in a virtual quadrupole rod ion optical system and found that, unlike the normal quadrupole rod ion optical system, the virtual quadrupole rod ion optical system creates an electric field that abundantly contains not only the quadrupole component but also higher-order multipole components. This finding suggested that, if the quadrupole component of the electric field can be suppressed to relatively increase the higher-order multipole components, it will be possible to create a system having only four poles yet capable of achieving ion optical characteristics comparable to those of a system with eight or more poles.
In the virtual multipole rod ion optical system, each virtual rod electrode is composed of a plurality of plate electrodes, and this structural characteristic allows different voltages to be respectively applied to the plate electrodes belonging to one virtual rod electrode. As stated previously, this idea has already been realized as far as the DC voltage is concerned; that is, the DC voltage is varied in a stepwise manner with the movement of the ions. However, the radio-frequency voltage for oscillating the ions is uniformly applied. Focusing on this point, the present inventors have reached the technique of suppressing lower-order radio-frequency components and increasing higher-order radio-frequency components by varying the phase of the higher-order radio-frequency voltage applied to the plate electrodes forming one virtual rod electrode. Computational simulations have confirmed that this technique can produce adequate effects with a practically feasible system configuration. Thus, the present invention has been obtained.
That is, the present invention aimed at solving the aforementioned problems is a mass spectrometer having an ion optical system for transporting ions to the next stage, which is characterized in that the ion optical system includes:
a) a virtual multipole rod ion optical element having 2×N pieces of virtual rod electrodes (where N is an integer equal to or greater than two) arranged so as to surround an ion beam axis, each virtual rod electrode being composed of M pieces of plate electrodes spaced along the ion beam axis (where M is an integer equal to or greater than three); and
b) a voltage-applying means for applying radio-frequency voltages in the following manner: in each set of the 2×N plate electrodes arranged around the ion beam axis, the same radio-frequency voltage is applied to any two plate electrodes opposing each other across the ion beam axis, and two radio-frequency voltages having the same amplitude and a phase difference of 180 degrees are respectively applied to any two plate electrodes neighboring each other around the ion beam axis; and in each set of the M plate electrodes forming one virtual rod electrode, the phase of the radio-frequency voltage applied to at least one of the plate electrodes is different from the phase of the radio-frequency voltage applied to another plate electrode.
The voltage-applying means may apply, to each plate electrode, not only the radio-frequency voltage but also a DC voltage, such as a bias voltage, superimposed on the radio-frequency voltage.
The ion beam axis does not need to be a linear axis; it may be polygonal or curved, according to which virtual rod electrodes may also have a polygonal or curved shape.
For example, when N=2, the ion optical element becomes a virtual quadrupole rod electrode. In this case, the quadrupole component of the electric field is maximized when the radio-frequency voltages applied to one virtual rod electrode are identical (i.e. when they have the same amplitude and phase). On the other hand, when a radio-frequency voltage having a different phase is applied to some of the plate electrodes, the quadrupole component of the electric field is decreased at least within the region near the plate electrodes to which the aforementioned radio-frequency voltage having the different phase is applied; instead, an electric-field component having a larger number of poles increases. Increasing the amount of the quadrupole electric-field component improves the ion beam convergence, and increasing an electric-field component whose number of poles is greater than four improves the ion transmission efficiency and ion acceptance. Accordingly, by decreasing the quadrupole component of the electric field to increase higher-order multipole components within some region in the aforementioned manner, one can improve the ion transmission efficiency and ion acceptance within a space around that region.
In the mass spectrometer according to the present invention, even if a virtual rod ion optical system having a quadrupole or similar low-order multipole configuration is used, the ion transmission efficiency, ion acceptance and other system performances can be improved over the entire system or within a local region along the ion beam axis. This makes it possible to adjust the ion optical characteristics so that the ion can be transported in the most appropriate manner according to the installation environment of the ion optical system, the conditions before and after the ion optical system, and other factors. For example, the transmission efficiency and acceptance of the ions may be regarded as important at an ion-inlet region, while the ion convergence may be given the first priority at an ion-exit region. In this manner, the amount of objective ions that will eventually reach an ion detector can be increased so as to attain high levels of detection sensitivity.
As one mode of the present invention, it is preferable that the voltage-applying means applies a radio-frequency voltage having the same amplitude as that of the radio-frequency voltage applied to another plate electrode and a phase difference of 180 degrees, to at least one of the M pieces of the plate electrodes forming each virtual rod electrode.
Applying radio-frequency voltages having a phase difference of 180 degrees (i.e. with reversed polarities) to the plate electrodes neighboring each other along the ion beam axis is highly effective in cancelling the quadrupole component of the electric field. In the present invention, two kinds of radio-frequency voltages having the same amplitude and a phase difference of 180 degrees are originally prepared as the voltages to be applied to the 2×N plate electrodes arranged so as to surround the ion beam axis, and these voltages can also be directly used in the present case. Therefore, modifying a conventional virtual multipole rod ion optical system to the present invention can be achieved by simply changing the wiring connections for supplying the voltages to the plate electrodes. Thus, it is possible to minimize the cost increase.
As a preferable mode of the present invention, the voltage-applying means may be configured so that radio-frequency voltages having a phase difference of 180 degrees are alternately applied for every group consisting of one or more of the plate electrodes neighboring each other along the ion beam axis at least in a part of the M-piece plate electrodes forming each virtual rod electrode.
The number of plate electrodes neighboring each other along the ion beam axis constituting a group for which the phase of the radio-frequency voltage is inverted from another group can be determined according to the required ion optical characteristics. Choosing a smaller number results in a larger decrease in the quadrupole component of the electric field and a larger increase in the higher-order multipole components. However, the number of plate electrodes to form one virtual rod electrode and the number of mutually neighboring plate electrodes to which the radio-frequency voltage with the same phase is applied must be appropriately selected so as to ensure the periodicity of the phase inversion of the radio-frequency voltages. It is normally necessary to increase the former number with an increase of the latter.
In the mass spectrometer according to the present invention, it is possible that the M pieces of the plate electrodes forming each virtual rod electrode include an electrode group in which the radio-frequency voltages having a phase difference of 180 degrees is alternately applied for every first number of plate electrodes neighboring each other along the ion beam axis, and another electrode group in which the radio-frequency voltages having a phase difference of 180 degrees is alternately applied for every second number of plate electrodes neighboring each other along the ion beam axis, where the second number differs from the first number.
In this case, there are two or more phase inversion periods of the radio-frequency voltages when viewed along the direction of the ion beam axis. Since these periods also affect the ion optical characteristics, it is possible to appropriately adjust the location and/or period of the phase inversion according to the usage environment of the ion optical system and the conditions before and after the ion optical system so as to optimize the ion optical characteristics.
In the mass spectrometer according to the present invention, it is possible that the M pieces of the plate electrodes forming each virtual rod electrode include an electrode group in which the radio-frequency voltages having a phase difference of 180 degrees are alternately applied for every predetermined number of plate electrodes neighboring each other along the ion beam axis, and another electrode group in which the same radio-frequency voltage is applied.
When viewed along the direction of the ion beam axis, this configuration can be regarded as a hybrid of a virtual multipole rod ion optical system characteristic of the present invention and a conventional virtual multipole rod ion optical system. This configuration also allows the location and/or period of the phase inversion to be appropriately adjusted according to the usage environment of the ion optical system and the conditions before and after the ion optical system so as to optimize the ion optical characteristics.
In the present invention, N may be any number equal to or greater than two. However, taking into account the cost and the required ion optical characteristics, it is practically recommended to choose N=2, i.e. to adopt the configuration of a virtual quadrupole rod ion optical system.
Similarly, there is no specific limitation on M. However, it is necessary to take into account the aforementioned periodicity of the phase inversion of the radio-frequency voltages in the direction of the ion beam axis. Furthermore, when considering the ion optical characteristics, it is often recommended to exclude the plate electrodes at both ends of the virtual rod electrode since the radio-frequency electric field created by these plate electrodes does not have an ideal profile. Accordingly, as one mode of the present invention, it is preferable that: the voltage-applying means is configured so that the radio-frequency voltages having a phase difference of 180 degrees are alternately applied for each of the plate electrodes neighboring each other along the ion beam axis at least in a part of the M-piece plate electrodes forming each virtual rod electrode; and M is equal to or greater than four.
The ion optical system as the characteristic element of the present invention can be used in various sections of the mass spectrometer in which ions need to be transported to subsequent stages. The system is particularly useful when different ion optical characteristics are required at the inlet and outlet sides or when it is necessary to transportions under harsh conditions, e.g. under a relatively low degree of vacuum.
Specifically, the mass spectrometer according to the present invention may include an ion source for ionizing a sample component under approximately atmospheric pressure and a mass separator for separately detecting ions according to their mass under high vacuum, with one or more intermediate vacuum chambers provided between the ion source and the mass separator, the ion source communicating with the intermediate vacuum chamber next to it via either a small ion-passage hole or a thin ion-passage pipe, and the ion optical system being placed within this intermediate vacuum chamber.
In this case, atmospheric gas flows from the ion source into the intermediate vacuum chamber via the ion passage hole or ion passage pipe. The ions conveyed by this gas tend to widely spread after being introduced into the intermediate vacuum chamber. However, these ions can be efficiently accepted into and transported within the ion optical system by suppressing the quadrupole component of the electric field and increasing the higher-order multipole components at the inlet side of the ion optical system so as to improve the ion transmission efficiency and the ion acceptance. At the outlet side of the ion optical system, the quadrupole component of the electric field can be relatively increased to enhance the ion convergence so as to minimize the loss of the ions at the micro-sized ion-passage hole. In this manner, the ion transmission efficiency can be generally improved and a higher level of ion-detection sensitivity can be attained.
The mass spectrometer according to the present invention may also include a collision chamber placed under a high vacuum atmosphere, the collision chamber being used for dissociating an ion by bringing the ion into collision with a collision-induced dissociation gas supplied into the collision chamber, and the ion optical system being placed within this collision chamber.
By this configuration, a precursor ion that has been mass-separated by a quadrupole mass filter or similar device in the previous stage can be efficiently introduced and dissociated by collision-induced dissociation, and the product ions thereby created can be converged close to the ion beam axis to be efficiently introduced into a quadrupole mass filter or similar device in the next stage. As a result, the detection sensitivity of the product ions improves, which contributes to an improvement in the accuracy of the qualitative and structural analyses of an objective sample component.
The basic configuration and operational principle of the ion optical system in the mass spectrometer according to the present invention is hereinafter described by means of
The present ion optical element 1 is composed of a plurality of electrode sets (eight sets in the present embodiment) arranged along the ion beam axis C (z-direction), each electrode set consisting of plate electrodes (e.g. 111, 121, 131 and 141) symmetrically arranged around the ion beam axis C at angular intervals of 90 degrees in an x-y plane perpendicular to the ion beam axis C. The plate electrodes are rectangular members made of a metal or another material having an electrical conductivity comparable to a metal, having the same thickness and a width of 2r. The distance between any two plate electrodes neighboring each other along the ion beam axis C (e.g. the plate electrodes 111 and 112) is a constant value of d. This ion optical element 1 can also be regarded as a structure consisting of four virtual rod electrodes 11, 12, 13 and 14 surrounding the ion beam axis C, each virtual rod electrode (e.g. 11) being composed of eight plate electrodes (e.g. 111, 112, . . . and 118) arranged parallel to the ion beam axis C. As shown in
As shown in
In the case of a conventional virtual multipole rod ion optical system, as shown in
In the ion optical system of the present embodiment, the radio-frequency voltages are applied, as described previously, in a manner totally different from the conventional method, whereby a radio-frequency electric field having a profile (potential gradient) entirely different from the conventional case is created in the space surrounded by the four virtual rod electrodes 11, 12, 13 and 14. This naturally causes a change in the action or effect on the ions. This point is hereinafter explained.
As will be described later, a DC voltage may be superimposed on the radio-frequency voltages applied to each plate electrode of the ion optical system 1. However, the following description initially ignores the DC voltage since it is for the moment unnecessary to consider the effect of the DC electric field.
A comparison is hereinafter made between the potentials in the radio-frequency electric fields respectively created by the conventional ion optical system shown in
It is commonly known that a potential created by multipole rod electrodes can be expressed by the following multipole expansion:
Φ(r,Θ)=ΣKn·(r/R)n·cos(nΘ) (1),
where Σ is the sum for all the values of n, which is a positive integer representing the order of the multipole electric field. Kn is the expansion coefficient representing the magnitude of the 2n-pole component of the electric field, and R is the radius of the inscribed cylinder A. The magnitude of the quadrupole component of the electric field is given by K2, i.e. the expansion coefficient for n=2. The orders of the higher-order multipole electric-field components having the symmetry of quadrupole are n=6, 10, 14, . . . , and 2(2k−1).
The expansion coefficients K2 obtained by numerical calculations for the ion optical system of the present embodiment and the conventional ion optical system are shown in
As is evident from
This result demonstrates that the quadrupole component of the electric field created by the ion optical system of the present embodiment is reduced from the levels in the conventional case. Since the ion transmission/storage efficiency of the quadrupole electric field is more dependent on the mass than that of the higher-order multipole electric fields, it is expected that using the ion optical system of the present embodiment will make the ion transmission/storage efficiency less dependent on the mass than ever before.
In general, the motion of an ion in a radio-frequency electric field can be separated into a micro oscillation, which depends on the frequency of the radio-frequency electric field, and a secular motion, which is independent of that frequency. On a macroscopic level, the ion's motion is represented by the secular motion, in which case a physical quantity called “pseudopotential” can be derived as a potential that determines the secular motion. That is to say, the ion optical characteristics of an ion optical system creating a radio-frequency electric field can be qualitatively understood by analyzing the pseudopotential.
Furthermore,
The previous analysis of the pseudopotential suggests that the ion optical system of the present embodiment has a significant ion-confining effect in the space between the plate electrodes neighboring each other along the ion beam axis C and is highly suitable for the transport and/or storage of ions. On the other hand, as is evident from the shape of the pseudopotential, the conventional ion optical system can confine ions into narrower spaces. Therefore, it can be said that the conventional structure is advantageous in ion-converging capability.
The present inventors have calculated the ion transmission efficiency by a computer simulation to confirm the superiority of the ion optical system of the present embodiment in terms of the ion transport/storage capability. In this simulation, the ion transmission efficiency was calculated by computing 100 ion trajectories and counting the number of ions arriving at predetermined points in both the ion optical system of the present embodiment and the conventional ion optical system. Any ion whose trajectory was diverted to the outside of the inscribed cylinder A before arriving at the predetermined points was regarded as a lost ion. The initial conditions of the ions were created by random numbers, and their initial positions were set to be approximately as large as the inscribed cylinder A. These strict initial conditions were intended to prevent the ion transmittance efficiency from reaching 100%. Naturally, the amplitude and frequency of the radio-frequency voltages were common to both the ion optical system of the present invention and the conventional ion optical system.
The previously described results lead to the conclusion that, as compared to the conventional ion optical system, the ion optical system according to the present invention can attain higher ion transmission/storage efficiencies and thereby enhance the detection sensitivity. Furthermore, it can also improve the mass dependency of the detection sensitivity.
One example of the mass spectrometer using the previously described characteristic ion optical system is hereinafter described with reference to the drawings.
This mass spectrometer 2 is a multi-stage differential pumping system having an ionization chamber 20 at approximately atmospheric pressure and an analysis chamber 29 evacuated by a high-performance vacuum pump (not shown) to maintain a high vacuum atmosphere, with a first intermediate vacuum chamber 23 and a second intermediate vacuum chamber 27 provided between them. The ionization chamber 20 communicates with the first intermediate vacuum chamber 23 through a thin desolvation pipe 22. The first intermediate vacuum chamber 23 communicates with the second intermediate vacuum chamber 27 through a small-sized passage hole 26.
The sample solution is sprayed from an electrospray ionization (ESI) nozzle 21 into the ionization chamber 20 maintained at approximately atmospheric pressure while being supplied with electric charges from that nozzle, whereby the sample components are ionized. Instead of the electrospray ionization method, an atmospheric pressure chemical ionization or other kinds of atmospheric pressure ionization methods may be used to ionize sample components. The ions produced within the ionization chamber 20 and the micro droplets from which the solvent has not been completely vaporized are drawn into the desolvation pipe 22 due to the pressure difference. While passing through the heated desolvation pipe 22, the solvent in the micro droplets is further vaporized and the ionization is promoted.
Inside the first intermediate vacuum chamber 23, a first ion guide 24 and an electrostatic lens 25, which correspond to the ion optical system in the present invention, are arranged along the ion beam axis C. The ions travel through the first ion guide 24 and the electrostatic lens 25 and then pass through the passage hole 26 to enter the second intermediate vacuum chamber 27. The second intermediate vacuum chamber 27 contains a second ion guide 28 composed of eight rod electrodes arranged so as to surround the ion beam axis C. The ions are converged by the second ion guide 28 and sent into the analysis chamber 29. The analysis chamber 29 contains a quadrupole mass filter 31 composed of four rod electrodes and a pre-rod electrode 30 located before the mass filter 31. The pre-rod electrode 30 is composed of four rod electrodes having a shorter length in the direction of the ion beam axis C. Among various kinds of ions, only the ion having a specific mass-to-charge ratio m/z can pass through the quadrupole mass filter 31 and reach the ion detector 32. The ion detector 32 produces a current signal corresponding to the number of received ions and outputs this signal as a detection signal.
A voltage created by adding a radio-frequency voltage generated by a radio-frequency (RF) voltage generator 35 and a DC voltage generated by a DC-voltage generator 36 is applied from an adder 37 to each plate electrode of the first ion guide 24. These correspond to the voltage-applying means in the present invention. Naturally, the present system has more power sources for appropriately applying either a voltage composed of a radio-frequency voltage and a DC voltage or a pure DC voltage to the desolvation pipe 22, electrostatic lens 25, second ion guide 28, pre-rod electrode 30, quadrupole mass filter 31 and other elements, although these power sources are not shown in the drawings.
The pressure difference between the ionization chamber 20 and the first intermediate vacuum chamber 23 is so large that the gas exiting from the mouth of the desolvation pipe 22 generates a turbulent flow having a velocity significantly disordered in irregular directions away from the ion beam axis C. Therefore, the first ion guide 24 needs to have a high level of ion transmission/storage capability. Furthermore, the first ion guide 24 also needs to have an excellent ion-converging capability to prevent the loss of ions at the small-sized passage hole 26 provided between the first intermediate vacuum chamber 23 and the second intermediate vacuum chamber 27. It has conventionally been difficult to achieve both a high ion transmission/storage efficiency and a high ion convergence. This difficulty can be overcome by using the first ion guide 24, which is based on the principle of the present invention.
In the first ion guide 24, the number of plate electrodes arrayed along the ion beam axis C, i.e. the number of electrode sets, is 12. However, the phase inversion of the radio-frequency voltage for each plate electrode is not made over the entire array; the ion optical system of the previously described embodiment is adopted only in the first half. That is to say, in the first half 241 which is close to the exit port of the desolvation pipe 22 (the upstream side of the ion stream), e.g. at the six plate electrodes 111, 112, 113, 114, 115 and 116 belonging to one virtual rod electrode, the phase of the radio-frequency voltage is changed by 180 degrees for each plate electrode in the direction of the ion optical axis C. When this first half 241 is separately viewed, its configuration is basically the same as shown in
On the other hand, in the second half 242 which is close to the passage hole 26 leading to the second intermediate vacuum chamber 27 (the downstream side of the ion stream), e.g. at the six plate electrodes 117, 118, 119, 11A, 11B and 11C belonging to one virtual rod electrode, a radio-frequency voltage having the same phase is applied to all the plate electrodes arrayed along the ion beam axis C. That is, the second half is the same as the conventional ion optical system shown in
As described thus far, the first ion guide 24 in the present example is divided into the first half 241 and the second half 242, each having different ion optical characteristics. By this configuration, the overall ion transport efficiency can be considerably improved.
The first intermediate vacuum chamber 23 is a region where the degree of vacuum is not very high and the ions significantly lose their energy due to collision with a neutral gas. Accordingly, the electrostatic lens 25, to which only a DC voltage is applied, is provided after the first ion guide 24 in order to increase the ion extraction efficiency. Due to the collision with the neutral gas, the ions are instantaneously cooled to the temperature of the neutral gas. As a result, in the vicinity of the electrostatic lens 25, the ions describe trajectories that approximately coincide with the lines of electric force. Therefore, it is possible to improve the ion extraction efficiency by appropriately setting the distribution of the DC voltage generated by the electrostatic lens 25.
In the mass spectrometer 2 of the previous example, there is no specific limitation on the method of ionization in the ionization chamber 20. The first ion guide 24 will exhibit its effect even if the electrospray ionization source is replaced by an atmospheric pressure chemical ionization source, atmospheric pressure photoionization source or any other kind of atmospheric pressure ionization source.
As is evident from the previous example, it is unnecessary to apply the design of the ion optical system of the embodiment shown in
The number of plate electrodes arrayed along the ion beam axis C (the number of electrode sets) is not limited to specific values. However, since an actually generated radio-frequency electric field is disordered at both (inlet and outlet) ends of the virtual rod electrodes, it is desirable to have a few or more plate electrodes arrayed along the ion beam axis C so as to create a stable radio-frequency electric field in which the aforementioned influence of the quadrupole electric-field component is reduced. The number of plate electrodes arranged in the x-y plane may not be four but any even number greater than four.
In the ion optical system of the previously described embodiment and the first half of the ion guide shown in the previous example, the phase of the radio-frequency voltage was inverted for every plate electrode along the ion beam axis C. However, it is also possible to invert the phase of the radio-frequency voltage for every two or more plate electrodes. An ion optical element according to one example of this case is shown in
In this example, radio-frequency voltages V·cos ωt and V·cos(ωt+π) are alternately applied for every two plate electrodes neighboring each other along the ion optical axis C. For example, in one virtual rod electrode, radio-frequency voltages V·cos ωt having the same phase are applied to the plate electrodes 111 and 112, while radio-frequency voltages V·cos(ωt+π) having a phase shift of 180 degrees are applied to the neighboring plate electrodes 113 and 114. This can be regarded as a system in which the phase inversion cycle of the radio-frequency voltage in the direction of the ion beam axis C is set larger than in the case of
Of course, one can freely design the combination of phase inversion cycles in one virtual rod electrode. Therefore, it is possible to arrange any number of different phase inversion cycles in any order.
In International Patent Application No. PCT/JP2008/000043, the applicant of the present patent application proposed the idea of changing the thickness of the plate electrodes, the intervals between the electrodes neighboring each other, and other elements of the geometrical structure so as to relatively decrease the quadrupole component of the electric field and thereby increase higher-order multipole components. This technique can be combined with the present invention, in which case the ion optical characteristics can be adjusted even more flexibly and extensively.
An ion optical element according to another example is shown in
The plate electrodes can be arranged in many other forms.
The various modes of ion optical systems described thus far can be used not only in the first intermediate vacuum chamber of a mass spectrometer having an atmospheric pressure ionization interface but also in many other sections of a mass spectrometer.
A first quadrupole mass filter 40, a collision cell 41 and a second quadrupole mass filter 44 are provided in the moving direction of the ions. An ion guide 24 having the same structure as that of the previously described first ion guide is provided inside the collision cell 41. Various kinds of ions having different mass-to-charge ratios m/z are introduced into the first quadrupole mass filter 40, among which only an objective ion (precursor ion) having a specific mass-to-charge ratio is selected to pass through the filter and enter the collision cell 41 in the next stage, while the other ions are dissipated halfway. A collision-induced dissociation (CID) gas, such as argon gas, is introduced into the collision cell 41. When passing through an electric field created by the ion guide 24, the precursor ion collides with the CID gas and is thereby dissociated, producing various kinds of product ions. These product ions, along with the precursor ions that have not been dissociated, exit the collision cell 41 and are introduced into the second quadrupole mass filter 44, in which only a product ion having a specific mass-to-charge ratio is selected to pass through the filter and be detected by the ion detector 32.
The inside of the analysis chamber is in a high vacuum state, whereas, inside the collision cell 41, a low vacuum state is locally created due to the CID gas supplied into it. To prevent a decrease in the degree of vacuum in the inner spaces of the quadrupole mass filters 40 and 44 before and after the collision cell, the ion injection hole 42 and the ion ejection hole 43 of the collision cell 41 are small sized. Therefore, similar to the case of
As already noted, the ion optical characteristics of the present system can be adjusted with considerable flexibility and extensiveness by controlling the phase inversion cycle or combining it with a conventional ion optical system. Therefore, the present system can be utilized in various forms other than the aforementioned ones; for example, it can also be substituted for the pre-rod electrodes of a quadrupole mass filter.
It should be noted that the previously described examples are mere examples of the present invention, and any change, modification or addition appropriately made within the spirit of the present invention will be naturally included in the scope of claims of the present patent application.
| Filing Document | Filing Date | Country | Kind | 371c Date |
|---|---|---|---|---|
| PCT/JP2008/000451 | 3/5/2008 | WO | 00 | 8/30/2010 |
