Classifications

• • H—ELECTRICITY
  • H01—ELECTRIC ELEMENTS
  • H01J—ELECTRIC DISCHARGE TUBES OR DISCHARGE LAMPS
  • H01J49/00—Particle spectrometers or separator tubes
  • H01J49/004—Combinations of spectrometers, tandem spectrometers, e.g. MS/MS, MSn
• • G—PHYSICS
  • G01—MEASURING; TESTING
  • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
  • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
  • G01N27/62—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating the ionisation of gases, e.g. aerosols; by investigating electric discharges, e.g. emission of cathode
  • G01N27/622—Ion mobility spectrometry
  • G01N27/624—Differential mobility spectrometry [DMS]; Field asymmetric-waveform ion mobility spectrometry [FAIMS]

Definitions

• the present invention relates to an apparatus and method for separating ions, more particularly the present invention relates to an apparatus and method for separating ions based on the ion focusing principles of high field asymmetric waveform ion mobility spectrometry (FAIMS).
• FIMS high field asymmetric waveform ion mobility spectrometry
• IMS ion mobility spectrometry
• the ion drift velocity is proportional to the electric field strength at low electric field strength, for example 200 V/cm, and the mobility, K, which is determined from experimentation, is independent of the applied electric field. Additionally, in IMS the ions travel through a bath gas that is at sufficiently high pressure such that the ions rapidly reach constant velocity when driven by the force of an electric field that is constant both in time and location. This is to be clearly distinguished from those techniques, most of which are related to mass spectrometry, in which the gas pressure is sufficiently low that, if under the influence of a constant electric field, the ions continue to accelerate.
• FAIMS high field asymmetric waveform ion mobility spectrometry
• K h transverse field compensation ion mobility spectrometry
• K field ion spectrometry
• Ions are separated in FAIMS on the basis of a difference in the mobility of an ion at high field strength, K h , relative to the mobility of the ion at low field strength, K.
• the ions are separated because of the compound dependent behavior of K h as a function of the applied electric field strength.
• FAIMS offers a new tool for atmospheric pressure gas-phase ion studies since it is the change in ion mobility, and not the absolute ion mobility, that is being monitored.
• Ions are classified into one of three broad categories on the basis of a change in ion mobility as a function of the strength of an applied electric field, specifically: the mobility of type A ions increases with increasing electric field strength; the mobility of type C ions decreases; and, the mobility of type B ions increases initially before decreasing at yet higher field strength.
• the separation of ions in FAIMS is based upon these changes in mobility at high electric field strength.
• an ion for example a type A ion, which is being carried by a gas stream between two spaced-apart parallel plate electrodes of a FAIMS device. The space between the plates defines an analyzer region in which the separation of ions occurs.
• the net motion of the ion between the plates is the sum of a horizontal x-axis component due to the flowing stream of gas and a transverse y-axis component due to the electric field between the parallel plate electrodes.
• the term "net motion” refers to the overall translation that the ion, for instance said type A ion, experiences, even when this translational motion has a more rapid oscillation superimposed upon it.
• a first plate is maintained at ground potential while the second plate has an asymmetric waveform, V(t), applied to it.
• the asymmetric waveform V(t) is composed of a repeating pattern including a high voltage component, V ls lasting for a short period of time t 2 and a lower voltage component, V 2 , of opposite polarity, lasting a longer period of time t 1 .
• the peak voltage during the shorter, high voltage portion of the waveform is called the "dispersion voltage" or DV in this disclosure.
• positive ions of type A travel farther during the positive portion of the waveform, for instance ⁇ > d 2 , and the type A ion migrates away from the second plate.
• positive ions of type C migrate towards the second plate.
• a positive ion of type A is migrating away from the second plate, a constant negative dc voltage can be applied to the second plate to reverse, or to "compensate" for, this transverse drift.
• This dc voltage called the "compensation voltage” or CV in this disclosure, prevents the ion from migrating towards either the second or the first plate.
• the ratio of K h to K may be different for each compound.
• the magnitude of the CV necessary to prevent the drift of the ion toward either plate is also different for each compound.
• only one species of ion is selectively transmitted for a given combination of CV and DV.
• the remaining species of ions for instance those ions that are other than selectively transmitted through FAIMS, drift towards one of the parallel plate electrodes of FAIMS and are neutralized.
• the speed at which the remaining species of ions move towards the electrodes of FAIMS depends upon the degree to which their high field mobility properties differ from those of the ions that are selectively transmitted under the prevailing conditions of CV and DV.
• An instrument operating according to the FAIMS principle as described previously is an ion filter, capable of selective transmission of only those ions with the appropriate ratio of K h to K.
• the applied CV is scanned with time, for instance the CV is slowly ramped or optionally the CV is stepped from one voltage to a next voltage, and a resulting intensity of transmitted ions is measured. In this way a CV spectrum showing the total ion current as a function of CV, is obtained. It is a significant limitation of early FAIMS devices, which used electrometer detectors, that the identity of peaks appearing in the CV spectrum are other than unambiguously confirmed solely on the basis of the CV of transmission of a species of ion.
• the higher sensitivity of the cylindrical FAIMS is due to a two-dimensional atmospheric pressure ion focusing effect that occurs in the analyzer region between the concentric cylindrical electrodes.
• the radial distribution of ions should be approximately uniform across the FAIMS analyzer.
• the radial distribution of ions is not uniform across the annular space of the FAIMS analyzer region.
• those ions become focused into a band between the electrodes and the rate of loss of ions, as a result of collisions with the FAIMS electrodes, is reduced.
• the efficiency of transmission of the ions of interest through the analyzer region of FAIMS is thereby improved as a result of this two- dimensional ion focusing effect.
• the mirror image of a focussing valley is a hill-shaped potential surface.
• the ions slide to the center of the bottom of a focussing potential valley (2 or 3 -dimensions), but slide off of the top of a hill-shaped surface, and hit the wall of an electrode. This is the reason for the existence, in the cylindrical geometry FAIMS, of the independent "modes” called 1 and 2.
• Such a FAIMS instrument is operated in one of four possible modes: PI, P2, Nl, and N2.
• the "P” and “N” describe the ion polarity, positive (P) and negative (N).
• a further improvement to the cylindrical FAIMS design is realized by providing a curved surface terminus of the inner electrode.
• the curved surface terminus is continuous with the cylindrical shape of the inner electrode and is aligned co-axially with an ion-outlet orifice of the FAIMS analyzer region.
• the application of an asymmetric waveform to the inner electrode results in the normal ion-focussing behavior described above, except that the ion-focussing action extends around the generally spherically shaped terminus of the inner electrode. This means that the selectively transmitted ions cannot escape from the region around the terminus of the inner electrode. This only occurs if the voltages applied to the inner electrode are the appropriate combination of CV and DV as described in the discussion above relating to 2-dimensional focussing.
• the CV and DV are suitable for the focussing of an ion in the FAIMS analyzer region, and the physical geometry of the inner surface of the outer electrode does not disturb .this balance, the ions will collect within a three- dimensional region of space near the terminus.
• the force of the carrier gas flow tends to influence the ion cloud to travel towards the ion-outlet orifice, which advantageously also prevents the trapped ions from migrating in a reverse direction, back towards the ionization source.
• Ion focusing and ion trapping requires electric fields that are other than constant in space, normally occurring in a geometrical configuration of FAIMS in which the electrodes are curved, and/or are not parallel to each other.
• a non-constant in space electric field is created using electrodes that are cylinders or a part thereof; electrodes that are spheres or a part thereof; electrodes that are elliptical spheres or a part thereof; and, electrodes that are conical or a part thereof.
• various combinations of these electrode shapes are used.
• cylindrical FAIMS technology As discussed above, one previous limitation of the cylindrical FAIMS technology is that the identity of the peaks appearing in the CV spectra are not unambiguously confirmed due to the unpredictable changes in K h at high electric field strengths.
• one way to extend the capability of instruments based on the FAIMS concept is to provide a way to determine the make-up of the CV spectra more accurately, such as by introducing ions from the FAIMS device into a mass spectrometer for mass-to-charge (m/z) analysis.
• the ion focusing property of cylindrical FAIMS devices acts to enhance the efficiency for transporting ions from the analyzer region of a FAIMS device into an external sampling orifice, for instance an inlet of a mass spectrometer.
• This improved efficiency of transporting ions into the inlet of the mass spectrometer is optionally maximized by using a 3- dimensional trapping version of FAIMS operated in nearly trapping conditions.
• the ions that have accumulated in the three- dimensional region of space near the spherical terminus of the inner electrode are caused to leak from this region, being pulled by a flow of gas towards the ion-outlet orifice.
• the ions that leak out from this region do so as a narrow, approximately collimated beam, which is pulled by the gas flow through the ion-outlet orifice and into a small orifice leading into the vacuum system of a mass spectrometer.
• the resolution of a FAIMS device is defined in terms of the extent to which ions having similar mobility properties as a function of electric field strength are separated under a set of predetermined operating conditions.
• a high-resolution FAIMS device transmits selectively a relatively small range of different ion species having similar mobility properties
• a low-resolution FAIMS device transmits selectively a relatively large range of different ion species having similar mobility properties.
• the resolution of FAIMS in a cylindrical geometry FAIMS is compromised relative to the resolution in a parallel plate geometry FAIMS because the cylindrical geometry FAIMS has the capability of focusing ions. This focusing action means that ions of a wider range of mobility characteristics are simultaneously focused in the analyzer region of the cylindrical geometry FAIMS.
• a cylindrical geometry FAIMS with narrow electrodes has the strongest focusing action, but the lowest resolution for separation of ions.
• the focusing action becomes weaker, and the ability of FAIMS to simultaneously focus ions of similar high-field mobility characteristics is similarly decreased.
• the resolution of FAIMS increases as the radii of the electrodes are increased, with parallel plate geometry FAIMS having the maximum attainable resolution.
• the ions are focused into an imaginary cylindrical zone in space with almost zero thickness, or within a 3- dimensional ion trap, in reality it is well known that the ions are actually dispersed in the vicinity of this idealized zone in space because of diffusion. This is important, and should be recognized as a global feature superimposed upon all of the ion motions discussed in this disclosure.
• the ions occupy a smaller physical region of space if the trapping potential well is deeper.
• the flow of carrier gas is used to prevent the ions from being attracted to one of the electrodes, and further to carry ions entrained therein out of the trapping region for detection.
• the flow of carrier gas is optimized for separation of ions during the time that they are resident within the analyzer region, and not for extracting the ions subsequent to their separation. In some cases, therefore, it is possible that the carrier gas flow rate will be other than sufficient to extract the selectively transmitted ions from the focusing region near the ion outlet. It would be advantageous to provide a method and a system for increasing the efficiency of ion extraction from the FAIMS analyzer by diverting the ion flow substantially away from the focusing region.
• an apparatus for separating ions comprising: a high field asymmetric waveform ion mobility spectrometer including: two electrodes at least one of which is for receiving an asymmetric waveform electrical signal and for producing a field between the electrodes; an ion inlet; an analyzer region in communication with the ion inlet and defined by at least a first ion flow path between the two electrodes; and, an ion diverter separate from the two electrodes for diverting the ions from the ion flow path in a known fashion.
• a method for separating ions comprising the steps of: a) providing an asymmetric waveform and a direct-current compensation voltage to an electrode to form an electric field, the field for effecting a difference in net displacement between ions in a time of one cycle of the applied asymmetric waveform for effecting a first separation of the ions by forming a subset thereof; b) producing ions within an ionization source; c) transporting said produced ions through the electric field along at least a first ion flow path in a direction approximately transverse to the electric field; and, d) diverting the selectively transmitted ions relative to the ion flow path absent the step of diverting in a predetermined fashion after separation.
• Figure 1 shows three possible examples of changes in ion mobility as a function of the strength of an electric field
• Figure 2a illustrates the trajectory of an ion between two parallel plate electrodes under the influence of the electrical potential V(t);
• Figure 2b shows an asymmetric waveform described by V(t);
• Figure 3 shows a simplified block diagram of an analyzer region of a parallel plate
• Figure 4a shows a simplified block diagram of an analyzer region of an improved
• FIG. 4b shows a simplified block diagram of an analyzer region of an improved
• FAIMS device with at least an ion diverting device, as operating in a second mode, according to a first embodiment of the present invention
• Figure 4c shows a simplified block diagram of an analyzer region of an improved
• FIG. 4d shows a simplified block diagram of an analyzer region of an improved FAIMS device with at least an ion diverting device, as operating in a first mode, according to a second embodiment of the present invention
• Figure 4e shows a simplified block diagram of an analyzer region of an improved FAIMS device with at least an ion diverting device, as operating in a second mode, according to a second embodiment of the present invention
• Figure 4e shows a simplified block diagram of an analyzer region of an improved
• FIG. 4f shows a simplified block diagram of an analyzer region of an improved
• FIG. 5 shows a simplified block diagram of a modified analyzer region of an improved FAIMS device with at least an ion diverting device according to a fourth embodiment of the present invention
• Figure 6 shows a simplified block diagram of another modified analyzer region of an improved FAIMS device with at least an ion diverting device according to a fifth embodiment of the present invention
• Figure 7 shows a simplified block diagram of another cylindrical geometry FAIMS device with a ion diverting device according to a sixth embodiment of the present invention
• Figure- 8 shows a simplified block diagram of another cylindrical geometry FAIMS device with a ion diverting device according to a seventh embodiment of the present invention
• Figure 9 shows a simplified block diagram of a cylindrical geometry FAIMS device with another ion diverting device according to a seventh embodiment of the present invention.
• FIG. 1 shown are three possible examples of the change in ion mobility properties with increasing electric field strength, as was discussed previously.
• the separation of ions in FAIMS is based upon a difference in these mobility properties for a first ion relative to a second ion.
• a first type A ion having a low field mobility K 1; ⁇ 0 w is other than separated in a FAIMS device from a second type A ion having a second different low field mobility K 2 _ ⁇ OW5 if under the influence of high electric field strength, the ratio K 1; high K l3 ⁇ o is equal to the ratio K 2;h ig h K 2j iow Interestingly, however, this same separation is achieved using conventional ion mobility spectrometry, which is based on a difference in ion mobilities at low applied electric field strength.
• FIG. 2a shown is a schematic diagram illustrating the mechanism of ion separation according to the FAIMS principle.
• An ion 1 for instance a positively charged type A ion, is carried by a gas stream 2 flowing between two spaced apart parallel plate electrodes 3 and 4.
• One of the plates 4 is maintained at ground potential, while the other plate 3 has an asymmetric waveform described by V(t), applied to it.
• the peak voltage applied during the waveform is called the dispersion voltage (DV), as is shown in Figure 2b.
• the waveform is synthesized so that the electric fields during the two periods of time thi h and ti o are not equal.
• Kh and K are identical at high and low fields, the ion 1 is returned to its original position at the end of one cycle of the waveform. However, under conditions of sufficiently high electric fields, K h is greater than K and the distances traveled during t ig and tj ow are no longer identical.
• the ion 1 experiences a net displacement from its original position relative to the plates 3 and 4 as illustrated by the dashed line 5 in Figure 2a.
• a constant negative dc compensation voltage CV is applied to plate 3 to reverse or "compensate" for this offset drift.
• the ion 1 does not travel toward either plate.
• two species of ions respond differently to the applied high electric field, for instance the ratios of K h to K are not identical, the compensation voltages necessary to prevent their drift toward either plate are similarly different.
• the compensation voltage is, for example, scanned to transmit each of the components of a mixture in turn. This produces a compensation voltage spectrum, or CV spectrum.
• FIG. 3 a simplified block diagram of a parallel plate FAIMS device according to the prior art is shown generally at 10.
• the analyzer region is defined by a space 16 between two flat, parallel plate electrodes 3 and 4, and between an ion-inlet electrode 6 having an ion-inlet orifice 19 and an ion-outlet electrode 8 having an ion-outlet orifice 21.
• the electrodes 3 and 4 are connected to an electrical controller 7 such that, in use, an asymmetric waveform and a superimposed dc compensation voltage is applied to electrode 3.
• the electrode 4 is maintained at a same dc voltage relative to each of the ion-inlet electrode 6 and the ion-outlet electrode 8.
• the asymmetric waveform and CV are set so that a particular species of positively charged ion (not shown) is transmitted through the analyzer region within space 16 between the plates 3 and 4, for instance the CV is negative, and the waveform has positive polarity.
• the "net" ion trajectory through the analyzer region is indicated in Figure 3 by dotted line 18.
• the powered electrode 3 is attracting the positive ion toward itself due to the negative dc bias, as indicated in Figure 3 by the arrowheads of the electric force lines that are directed toward electrode 3.
• the effect of the asymmetric waveform is to push the ion away from the electrode 3, as is indicated in Figure 3 by the arrowheads of the electric force lines that are directed away from electrode 3.
• This balanced condition is shown schematically in Figure 3 as a series of double-headed electric force lines, comprising a DV and CV component, which are selected for transmitting ions having specific high field mobility properties.
• the fields are not strong everywhere around the powered electrode 3.
• the fields are strong and the balanced condition exists.
• the electric field strength changes such as occurs on a side 3b of the powered electrode 3 at the end edges of the electrode facing one of the ion-inlet electrode 6 and the ion-outlet electrode 8
• Figures 4c to 4f show different modes of operation of a same electrode geometry as shown Figure 4a, wherein different combinations of applied voltages are described. Therefore, reference numerals indicating elements of the drawings identical to those elements previously described with reference to Figure 4a have been omitted from Figures 4b to 4f in the interest of clarity and brevity.
• an ion-inlet electrode 131 and an ion-outlet electrode 132 have similarly been omitted from Figures 4b to 4f, but are understood to have a crucial role in producing the strong electric fields that are described subsequently for each mode of operation with reference to Figures 4b to 4f.
• ions are shown schematically in Figures 4a to 4f (not to scale) as circles in which a '+' sign appears to indicate ion species of positive polarity charge, and as circles in which a '-' sign appears to indicate ion species of negative polarity charge. Circles having a dark boarder are used in some cases, for instance to distinguish between two ions having a same charge but having different mobility properties as a function of electric field strength.
• the analyzer region includes a first electrode 121, a second electrode 122, a third electrode 123, a fourth electrode 124 and a fifth electrode 125 in a substantially uniformly spaced-apart stacked arrangement.
• two spaces 126a and 127a are disposed on a first side of electrode 123 and two different spaces 126b and 127b are disposed on the opposite side of electrode 123.
• the electrodes shown in Figure 4a are flat parallel plates with square ends.
• a CV and DV is applied to the third electrode 123, while the second electrode 122 and the fourth electrode 124 are maintained at ground potential or some other dc potential.
• ions are drawn to the third electrode 123 due to the dc bias, and are carried by the uniform gas flow predominantly through spaces 127a and 127b. Since the electrodes are flat parallel plates the electric fields within each space 127a and 127b are constant, such that ion focusing does not occur. Additionally the electric fields are the same within each space, such that a same ion is selectively transmitted through both spaces 127a and 127b. Of course, the electrodes are mounted in an insulating support, which is omitted for clarity in Figure 4a. Each space 126a, 127a, 127b and 126b defines a separate ion flow path that is closed on four sides such that it is other than possible for ions to move from one space to the other space. Further, a physical barrier (not shown) " is provided along the outer surfaces of electrodes 121 and 125 for preventing the flow of carrier gases through spaces other than 126a, 127a, 127b and 126b.
• electrode 123 is connected to an electrical controller (not shown) such that, in use, an asymmetric waveform and a superimposed first dc voltage, wherein the superimposed first dc voltage is other than the compensation voltage, is applied to the electrode 123.
• the electrodes 122 and 124 are connected to at an electrical controller (not shown), such that, in use, electrodes 122 and 124 are maintained at a predetermined second dc voltage or at a ground potential.
• the ion- inlet electrode 131, having an ion-inlet orifice 135 therethrough, and an ion-outlet electrode 132, having an ion-outlet orifice 136 therethrough, are also maintained at predetermined dc voltages by power supplies (not shown).
• the CV is the difference between the superimposed first dc voltage applied to the electrode 123 and the second dc voltage applied to the electrodes 122 and 124.
• Those ions having appropriate mobility properties for a particular combination of DV and CV are selectively transmitted through the analyzer region, for instance within space 127a between the electrodes 122 and 123, and within space 127b between the electrodes 123 and 124.
• the selective transmission of an analyte ion through the FAIMS analyzer region may require the electrode 123 to be biased 5 volts lower than electrodes 122 and 124, for instance the CV is negative 5 volts, and for the waveform to be of positive polarity, for example 2500 volts.
• the electrodes 121 and 125 are connected to at least a dc voltage controller, for instance two separate dc voltage controllers (not shown), such that, in use, electrodes 121 and 125 are maintained at a third predetermined second dc voltage or at ground potential.
• a 'net' trajectory for a selectively transmitted ion through the- FAIMS analyzer region is shown diagrammatically in Figure 4a at dotted lines 133 and 134.
• the powered electrode 123 is attracting the ions toward itself due to the negative dc bias relative to electrodes 122 and 124, as indicated in Figure 4a by the arrowheads of the electric force lines that are directed toward electrode 123.
• the effect of the asymmetric waveform is to push the ion away from the electrode 123, as is indicated in Figure 4a by the arrowheads of the electric force lines that are directed away from electrode 123.
• This balanced condition is shown schematically in Figure 4a as a series of double-headed electric force lines, comprising a DV and CV component that are selected for transmitting ions having specific high-field mobility properties.
• This balanced condition extends completely around the inlet end of the electrode 123 facing the ion-inlet electrode 131a and completely around the outlet end of the electrode 123 facing the ion-outlet electrode 132a.
• the electric fields extend on both sides of the third electrode 123 symmetrically within the analyzer region, such that the ion continues to "see” the same balancing electric forces and will continue along a stable trajectory to exit the analyzer.
• the electrical forces for selectively transmitting the ion remain balanced beyond the physical limit of the electrodes because the two sides of the powered third electrode 123 are symmetrical.
• a metal conductive surface of electrodes 122 and 124 is located a same distance from each surface of the powered third electrode 123. Under these conditions, even slowly flowing gas will tend to keep the ions positioned near the trailing edge of the electrode, in a position close to the ion-outlet electrode 132.
• the third electrode 123 of the system shown generally at 120 in Figure 4a is narrow relative to the spaces 127a and 127b between the electrodes, then the specific shape of the corners at the edges of the electrode plates will other than critically influence the ion trajectory. For instance rounded or squared corners behave more or less the same in terms of the resulting fields that the ion will experience in this region. This is because the electric fields tend to 'smooth' themselves out over a distance away from a corner of the electrode, such that effectively the fields around the electrode look exactly the same as if it was rounded once you move more than some distance away. If the electrode is thick, for example more than approximately 20% of the thickness of the spaces, then the shape is important. Also, if the ion trajectory is very close to the third electrode 123, a contour at an edge of the electrode has more influence on the path of travel than when the ions are further away from the third electrode 123.
• the ions would otherwise be trapped at the outlet edge of electrode 123, for example the ions are unable to move in any direction, absent a gas flow that is sufficiently strong to carry the ions to the ion-exit orifice.
• the dc voltage applied to the ion-exit electrode 132 is adjusted to help pull the ions away from the trailing edge of electrode 123 in a controlled fashion.
• the ions are detected by electrometric means (not shown) external to the analyzer region.
• electrodes 121 and 125 are connected to at least a dc controller, such that a dc bias is optionally applied to the first and fifth electrodes 121 and 125 for diverting the ions.
• positively charged ions are selectively transmitted through spaces 127a and 127b and collected at electrodes 121 and 125, which have a negative dc bias applied.
• a positive dc bias is applied to electrodes 121 and 125 for focusing the positively charged ions into a narrow beam exiting the analyzer region for highly efficient extraction, as shown for a second mode of operation in Figure 4b.
• the ion-outlet electrode 123 is additionally provided with an orifice for transmitting ions to a detector.
• a same combination of CV and DV are applied to the second elecfrode 122, and to the fourth electrode 124 while the first electrode 121, the third electrode 123 and the fifth electrode 125 are maintained at ground potential as shown at Figures 4c and 4d.
• the constant electric fields within the spaces 126a, 127a, 127b and 126b are identical, such that a same ion species is selectively transmitted through each of the four spaces.
• the ions will be distributed along four analyzer regions instead of only two, which reduces the space-charge induced ion-ion repulsion and minimizes ion losses in the analyzer region. Ion focusing occurs at the outlet edge of each powered electrode 122 and 124, as was previously discussed with reference to Figure 4b.
• a different combination of CV and DV are applied to the second electrode 122, and to the fourth electrode 124 while the first electrode 121, the third electrode 123 and the fifth electrode 125 are maintained at ground potential as shown in Figure 4d.
• the first, third and fifth electrodes are maintained at some other dc potential.
• Figure 4d illustrates a mode of operation wherein a positive polarity waveform and negative CV are applied to the second electrode 122, whereas a negative polarity waveform and positive CV are applied to the fourth electrode 124.
• positive ions are selectively transmitted through spaces 126a and 127a, whereas negative ions are selectively transmitted through spaces 127b and 126b.
• the current mode of operation selectively transmits a same species of positive ion within spaces 126a and 127a, since the electric fields are identical within the spaces 126a and 127a.
• a same species of negative ion is transmitted within spaces 126b and 127b, since the electric fields are identical within the spaces 126b and 127b.
• a dc potential is optionally applied to the third electrode 123 for diverting the ions in a predetermined manner.
• a same DV and CV combination are applied to the second and fourth electrodes 122 and 124 for selectively transmitting a same positive ion species.
• a positive dc potential applied to the ion diverter third electrode 123 will cause all ion trajectories to diverge away from the central axis of the device.
• a negative dc potential applied to ' the ion diverter third electrode 123 will cause all ion trajectories to diverge towards the central axis of the device, for instance the positive ions will be focused into a narrow beam coaxial with the center axis of the device. If a more negative dc potential is applied, then the positive ions are optionally collected and detected at the third elecfrode 123.
• the electric fields within spaces 126a and 127a are different, because on one side of the powered electrode 122 the compensation voltage is determined relative to a ground potential, whereas on the opposing side the compensation voltage is determined relative to a predetermined applied dc potential. Consequently, positive ions are transmitted through each space, however, a first species of positive ion is transmitted through spaces 126a and 126b, and a second different species of positive ion is transmitted through spaces 127a and 127b.
• FIG 4f an alternative mode of operation of the third embodiment is shown, wherein a different D V and C V combination is applied separately to the second and fourth electrodes 122 and 124.
• a positive polarity waveform and negative CV are applied to the second electrode 122
• a negative polarity waveform and positive CV are applied to the fourth electrode 124.
• positive ions are selectively transmitted through spaces 126a and 127a
• negative ions are selectively transmitted through spaces 127b and 126b.
• the FAIMS analyzer functions as a four- mode FAIMS device, characterized in that a first species of positive ion is transmitted through space 126a, a second different species of positive ion is transmitted through space 127a, a first species of negative ion is transmitted through space 127b, and a second different species of negative ion is transmitted through space 126b.
• a first species of positive ion is transmitted through space 126a
• a second different species of positive ion is transmitted through space 127a
• a first species of negative ion is transmitted through space 127b
• a second different species of negative ion is transmitted through space 126b.
• a positive dc potential applied to the ion diverter third electrode 123 causes the positive ions that are selectively transmitted through spaces 126a and 127a to diverge away from the third electrode 123 of the device, whereas the negative ions that are selectively transmitted through spaces 127b and 126b will see an attractive force and be diverted towards the third electrode 123 of the device.
• a negative dc potential applied to the ion diverter third electrode 123 causes the positive ions that are selectively transmitted through spaces 126a and 127a to diverge towards the third electrode 123 of the device, whereas the negative ions that are selectively transmitted through spaces 127b and 126b will see an repulsive force and be diverted away from the third electrode 123 of the device.
• a more positive dc bias toward electrode 123 it is possible to collect negative ions at electrode 123, with the positive ions being diverted more strongly.
• a more negative dc bias toward electrode 123 it is possible to collect positive ions at electrode 123, with the negative ions being diverted more strongly.
• the preferred embodiment of the present invention as described with reference to Figures 4c to 4f includes an electrode 123 for diverting ions, optionally other ion diverting means are used.
• a slit-shaped orifice including a gas jet is optionally provided in place of electrode 123 for providing a flow of gas for diverting the ions.
• the ion diverting gas flow augments the uniform gas flow that, in use, is moving through the analyzer region for carrying the ions in a direction transverse to the applied electric fields.
• the ion diverting gas flow is used to push ions from the analyzer region through an outlet for subsequent analysis or collection.
• the ion diverting gas flow diverts positively charged ions and negatively charged ions in a same direction, either away from the ion diverting means or towards the ion diverting means.
• the embodiments described with reference to Figures 4a to 4f have employed flat parallel plate electrodes with square end edges.
• the first to fifth electrode plates 121 to 125 are parallel flat-plate electrodes having a leading and a trailing edge, with respect to a direction of ion flow through the analyzer region when in use, that are rounded in cross section.
• the radius of curvature of the smooth curve provided at the leading and trailing edges of each electrode 121 to 125 are appropriate to focus and trap the ions at leading and trailing edges, and of course the electrode plates are thick enough to accommodate the radius of curvature.
• each of the first through fifth electrodes 121 to 125 are provided with leading and trailing edges that are rounded in cross sections, ion focusing will occur only at those electrodes to which a DV and superimposed CV are applied. .
• This focussing effect with flat-plate electrodes was disclosed in a copending PCT application in the name of R. Guevremont and R. Purves
• At least one of the leading edge and the trailing edge are further shaped with a concave smooth curve that is directed away from the direction of ion flow.
• the concave smooth curve at the at least an edge of the electrode plates is for producing electric fields that are shaped to direct the flow of ions generally inwardly towards the center of the electrode plate.
• the ions are focused into a narrow beam before entering the flat plate analyzer region, which minimizes ion losses during separation.
• the efficiency of ion extraction is improved at the trailing edge of the plate by focusing the ions further into a narrow beam prior to their extraction, thus maximizing ion transmission and minimizing overall losses.
• first through fifth elecfrode plates 121, 122, 123, 124 and 125 are curved, wherein the first through fifth curved electrode plates are referred to as 151, 152, 153, 154 and 155, respectively, for a fourth embodiment of the present invention as shown in Figure 5a.
• An ion-inlet electrode (not shown) and an ion-outlet electrode (not shown) are additionally provided at the ion-inlet and the ion-outlet edges, respectively, of the electrode plates 151, 152, 153, 154 and 155.
• the ion-inlet electrode and the ion-outlet electrode having an ion-inlet orifice and an ion-outlet orifice, respectively, each orifice being aligned with electrode plate 153.
• the ion- inlet electrode and the ion-outlet electrode play a crucial role in producing the high strength electric fields near the ion-inlet and ion-outlet edges, respectively, of the curved electrode plates.
• a curved electrode geometry produces non-constant electric fields, such that in the fourth embodiment of the present invention a focusing region exists within each space 156a, 157a, 157b and 156b.
• the field produced on one side of a powered electrode plate is other than identical to the field that is produced on the opposite side of the powered electrode plate.
• two different species of ions are typically transmitted; a first ion species within space 157a and a second ion species within space 157b.
• Electrode plate 153 is optionally shaped with curved ends for directing ions generally inwardly toward the center of the electrode edge. Further optionally, each of the other electrode plates 151, 152, 154 and 155 are also shaped for directing the ion trajectories.
• a fifth embodiment of the present invention having a lens shaped third electrode 163 is described.
• curved electrode geometry produces non-constant electric fields, such that in the fifth embodiment of the present invention a focusing region exists within each space 166a, 167a, 167b and 166b.
• an appropriate combination of DV and CV is applied to the electrode 163, identical electric fields that are non-constant in space are produced within spaces 167a and 167b, such that one species of ion is selectively transmitted.
• a combination of DV and CV is applied to elecfrodes 162 and 164.
• two-dimensional ion focusing does not occur within the spaces 126a, 127a, 127b and 126b when the electrodes 121, 122, 123, 124 and 125 are flat, parallel plate electrodes.
• the electrodes 121, 122, 123, 124 and 125 are flat, parallel plate electrodes.
• two-dimensional ion focusing does occur within the spaces 156a, 157a, 157b and 156b between the curved electrode plates 151, 152, 153, 154 and 155, shown in Figure 5a.
• a subset of ions having appropriate mobility properties are transmitted also, the two-dimensional ion focussing effect that exits between the curved electrode plates reduces significantly the range of appropriate mobility properties.
• a subset of ions including fewer different ion species are transmitted through an analyzer region between curved elecfrode plates, relative to the subset of ions that are transmitted through an analyzer region between flat, parallel plate electrodes.
• the analyzer regions according to the first, second and third embodiments of the present invention have a rotational axis of symmetry that is coaxial with the third electrode 123 and within the plane of the drawing. Rotation about this rotational axis of symmetry leads to a concentric cylinder FAIMS device, in which electrodes 121 and 125 form a continuous outer cylindrical surface 171, electrodes 122 and 124 form a continuous inner cylindrical surface 172 and electrode 123 forms an ion diverter 173 that is coaxially aligned with the outer and inner concentric cylinder elecfrodes 171 and 172, respectively.
• a single annular analyzer region 174 is defined by the space between the outer cylindrical electrode 171 and the inner cylindrical electrode 172.
• This is a sixth embodiment of the invention and will be described with reference to Figure 7.
• T ⁇ e CV and DV are applied to the inner cylindrical electrode 172 in the example that is illustrated in Figure 7; however, the CV and DV is alternatively applied to the outer cylindrical electrode 171. Since the same DV and CV must be applied to a cylindrical electrode, only one species of ion is transmitted through the analyzer region at one time.
• the ion diverter 173, in the form of a probe electrode, is shown at ground potential in Figure 7, however in practice the probe electrode 173 is biased at negative or positive dc.
• a negative dc bias applied between the probe electrode 173 and the inner cylindrical electrode 172 will divert ions toward the probe electrode 173. If the negative dc bias is strong enough, ions will impact the probe elecfrode and are optionally detected. Alternatively, if a positive dc bias applied between the probe electrode 173 and the inner cylindrical elecfrode 172, the positively charged ions will be diverted away from the probe elecfrode 173. With an appropriate negative dc bias, ions will be focused into a narrow beam substantially axially aligned with the probe electrode for extraction from the analyzer region through an ion outlet.
• the device shown generally at 170 in Figure 7 has an ion diverter 173 in the form of an orifice having a gas nozzle for directing a jet of gas along the central axis of the inner electrode 172.
• the ion diverting gas jet pushes ions away from the terminus of the inner cylinder for exfraction through an ion-outlet orifice (not shown) in an ion-outlet electrode (not shown).
• FIG. 8 shown is a simplified block diagram of a cylindrical geometry FAIMS device with an ion diverting device according to a seventh embodiment of the present invention.
• the seventh embodiment is very similar to the sixth embodiment, except the inner cylindrical electrode 208 is provided with a curved surface terminus 207, and the inner surface of the outer electrode 204 is shaped to maintain a substantially uniform distance to the inner cylindrical elecfrode 208 near the curved surface terminus 207.
• This geometry of FAIMS is referred to as a dome-FAIMS or dFAIMS.
• an ion diverter 210 in the form of a probe electrode whose outer surface is continuous with the outer surface of the inner elecfrode 208 only at a small region 209 near the tip of the inner electrode.
• the ion diverter 210 is coaxially aligned with the inner cylindrical electrode 208 and the outer cylindrical electrode 204, and with an ion-outlet orifice 217 in the outer cylindrical elecfrode 204. It should be noted that the ion diverter 210 is easily removed from the FAIMS apparatus when so desired.
• the ion diverter 210 is operated at a same voltage as the inner electrode 208, such that the electric fields near the terminus 207 are other than perturbed by the ion diverter 210.
• the device called dFAIMS is typically used in two fashions of operation. First, it is used for 3 -dimensional trapping, since the ions that are swept along the inner electrode 208 through space 206 arrive at the tip of the dome and are unable to proceed further because of the trapping action that extends along the sides of the inner electrode and around the tip of the electrode. This has been discussed in greater detail above with respect to Figure 4a.
• the device is optionally operated in continuous flow mode, if the electrode voltages are such that the stream of ions, which travel along the side of the inner electrode 208 through space 206, escape from the zone near the tip of the elecfrode. The ions tend to travel along the curved spherical surface of the inner electrode towards the central axis of the inner elecfrode 208, following the focusing fields, and are extracted as a narrow beam of ions.
• the dFAIMS is improved by the addition of a probe electrode, the ion diverter
• the inner electrode 208 in Figure 8, through the center of the inner electrode 208.
• the purpose of this electrode is to modify the electric fields near the terminus of the dome 207 of the inner electrode 208.
• the objectives are two-fold. First, the ions that accumulate near the terminus of 207 the inner electrode 208 are ejected or forced away from the inner electrode 208 by the repulsive forces of an electric field applied via a voltage on the probe electrode 210 relative to the inner electrode 208. Secondly, under some circumstances it is advantageous to pull the ions out of the trapping region towards this probe electrode 210.
• the probe electrode 210 is used, for example, to collect a sample of the ions that collide with the surface of the probe electrode 210 that is exposed and substantially continuous with the inner electrode 208 at the tip of the domed surface 207 of the inner electrode 208.
• the probe electrode 210 is supported and aligned by insulating materials, and extends to the surface 209, which is substantially continuous with the surface of the inner electrode 208.
• the asymmetric waveform that is applied to the inner electrode 208 through a connection screw (not shown) is also applied to the probe electrode 210.
• the probe electrode 210 does not contact the inner electrode 208, and a set of insulators (not shown) serve to suspend the probe electrode 210 away from the surfaces of the inner electrode 208.
• An additional electronic source (not shown) for applying a small dc bias between the probe electrode 210 and the inner electrode 208 is also provided.
• the space also serves as a conduit for an (optional) flow of gas.
• the gas flow serves several potential purposes. First, a gas flow traveling from the analyzer region into the channel between rod 226 and hole 227 serves to ensure that no contaminants are added to the analyzer region via this channel. If the gas flows into the channel, the flow will augment the existing flow along the analyzer region 206, and reduce the residence time of the ions inside the FAIMS, and bring the ions more quickly to the tip of the inner electrode 208.
• a second optional use for the gas flow through the hole 227 is also envisioned.
• the ions that are trapped in the region 216 are optionally reacted chemically with a gas that exits from the hole 227 in the tip of the inner electrode 208.
• a gas that reacts with an ion is carbon dioxide, which is known to form complexes with some types of ions. This new complex has different mobility properties compared to the bare ion, permitting that ion to leave the trapping region 216 for detection, even if another non-reactive ion resides in the trapping region 216.
• the reactant gas is optionally used to reject some unwanted ion by forming a complex whose properties of mobility at low and high fields are no longer appropriate for the storage of this ion under the prevailing conditions of CV and DV, thereby increasing the relative number of the of ions of interest within the trapping region.
• a third purpose for a gas flow out of the hole 227 in the inner elecfrode 208 is easily visualized.
• This gas flow is used to assist in ejecting ions out of the trapping region 216, if the flow along the analyzer region 206 is not sufficiently high for this purpose.
• the flow along the analyzer region 206 must in practice be set for the optimum separation of ions along the annular space between the outer electrode 204 and the inner electrode 208. This flow along the analyzer region 206 may not be the optimum flow necessary to move ions out of the dFAIMS at the tip of the inner electrode 208.
• a gas flow into or out of the hole 227 in the inner elecfrode 208 will serve to permit optimum flows both in the analyzer region 206 and out of the hole 217 in the outer electrode 204 which leads to an optional ion detection system (not shown).

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