Double-focusing mass spectrometer apparatus and methods regarding same

Information

  • Patent Grant
  • 6501074
  • Patent Number
    6,501,074
  • Date Filed
    Tuesday, October 19, 1999
    25 years ago
  • Date Issued
    Tuesday, December 31, 2002
    22 years ago
Abstract
A double-focusing mass spectrometer apparatus includes a first cylindrical sector electrode defined at a first radial distance from a axis with the first cylindrical sector electrode having an upper and lower edge and a second cylindrical sector electrode surface defined at a second radial distance from the axis with the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode. An ion path is defined between the first and second cylindrical sector electrodes. A first magnet pole and a second magnet pole are positioned proximate the upper and lower edges of the first and second cylindrical sector electrodes, respectively, for providing a magnetic field in the ion path. A first and second array of electrodes, e.g., cylindrical segment electrodes, are positioned between the upper edges and lower edges of the first and second cylindrical sector electrodes, respectively, for use with the first and second cylindrical sector electrodes to provide a desired electric field in the ion path perpendicular to the magnetic field. In one configuration, the first and second cylindrical sector electrodes may not be required to provided the desired electric field but the electric field may be provided by the arrays of electrodes alone. Generally, the electrode arrays can be configured in a number of ways with application of appropriate voltages to attain the desired electric field, e.g., electrodes evenly spaced between the upper edges of the first and second cylindrical sector electrodes and electrodes evenly spaced between the lower edges of the first and second cylindrical sector electrodes with a predetermined voltage applied that varies logarithmically across the first and second arrays of electrodes. Methods for use in double focusing mass spectrometry are also provided, e.g., methods to provide the above apparatus.
Description




FIELD OF THE INVENTION




The present invention relates to mass spectrometers, e.g., compact miniature mass spectrometers, for use in chemical analysis of samples. More particularly, the present invention pertains to mass spectrometers employing superimposed magnetic and electric fields.




BACKGROUND OF THE INVENTION




Various types of mass spectrometers are being used in the field of chemical analysis and related fields. For example, such mass spectrometers may include deflecting type mass spectrometers in which the ions constituting the ion beam are separated by a magnetic field according to their mass to charge (m/e) ratio. Deflecting-type mass spectrometers can broadly be classified into two categories, single-focusing and double-focusing mass spectrometers, according to the type of ion beam optical system employed. In the single focus category, directional focusing but not velocity focusing is possible, and in the double focus category, both directional and velocity focusing are possible.




In the past, generally, in conventional types of double-focusing mass spectrometers, the electric field and magnetic field used for deflection were arranged separately. However, in U.S. Pat. No. 3,984,682 to Matsuda, entitled “Mass Spectrometer With Superimposed Electric and Magnetic Fields,” issued Oct. 5, 1976, a mass spectrometer employing superimposed electric and magnetic fields arranged substantially at right angles to one another is described. As described in Matsuda, if the electric field of the superimposed fields is swept and the magnetic field of the superimposed fields is kept fixed, ions having different m/e ratios will satisfy the double focusing condition, and therefore, the ions can be collected at a detector. In such a case, the ratio of the voltage applied for establishing the electric field strength and the accelerating voltage must be kept constant during the sweeping of the electric field. Matsuda arranges cylindrical electrodes between magnetic poles such that the electric field of the device is perpendicular to the magnetic field to provide suitable x-y focusing. Further, in addition, auxiliary electrodes are arranged symmetrically above and below the cylindrical electrodes. Voltages corresponding to those applied to the cylindrical electrodes are applied to the auxiliary electrodes to control the shape of the electric field, particularly for controlling z-direction focusing. It is recognized in Matsuda that in the case of superimposed fields with the cylindrical electrodes arranged between the magnetic poles, that consideration must be given to the size of the cylindrical electrodes. In Matsuda, the ideal ratio of the distance between the cylindrical electrodes and their height is 1:2. However, having cylindrical electrodes of such a height adds to the size of the overall device and further decreases a desirably high magnetic field between the poles, i.e., the magnetic field decreasing as the height of cylindrical electrodes increases and the gap between the magnetic poles is increased.




Another mass spectrometer employing superimposed magnetic and electric fields is described in U.S. Pat. No. 4,054,796 to Naito, entitled “Mass Spectrometer With Superimposed Electric And Magnetic Fields,” issued Oct. 18, 1977. U.S. Pat. No. 4,054,796 describes the use of superimposed electric and magnetic fields arranged substantially at right angles. In U.S. Pat. No. 4,054,796, electrodes having concentric cylindrically shaped curved surfaces are used to form the electric field of the superimposed magnetic and electric fields, while magnetic pole pieces form a magnetic field perpendicular to this electric field. The superimposed fields are provided in an ion path in an airtight throughway. At one end of the ion path is an ionization chamber for providing an ionized specimen to the ion path. Electrodes producing a constant accelerating voltage (as opposed to a varying accelerating voltage as described in Matsuda) draw the ionized specimen into the ionization chamber in an ion path in which the superimposed fields are formed. At the other end of the ion path is an ion collector. The ions introduced into the superimposed fields in the ion path are deflected according to their mass to charge (m/e) ratios with such deflected ions being detected by the ion collector. In this mass spectrometer, the central orbit of the ion beam in the ion path (that is, the orbit of the ions of mass to charge ratio being detected) is located on an equipotential surface of the electric field. The intensity of the electric field in the ion path is swept (i.e., voltage on the cylindrical electrodes is varied) to change the mass to charge ratio of the ions traveling the central orbit. However, such sweeping of the electric field when the accelerating voltage is kept constant, is accompanied by an undesirable shift in the focusing position of the ion beam. The change in focusing position is compensated by a variety of techniques. For example, such compensation may be achieved by auxiliary electrodes placed above and below the curved surface electrodes. The voltage on the auxiliary electrode is varied as a function of the voltage applied to the curved surface electrodes.




Such existing mass spectrometers as described above are generally constructed in whole or in part with discrete metal electrodes and insulators assembled inside of a metal vacuum envelope. Due to such construction, the size of such existing mass spectrometers is generally large and the cost of such mass spectrometers prohibits their use for various functions, e.g., environmental monitoring, bedside patient care in hospitals, battlefield chemical and biological agent detection, chemical plant process control, etc.




Further, generally, as described above, one way of obtaining superimposed electric and magnetic fields is with the use of two cylindrical electrodes having the same cylinder axis, but different radii. If the axial height of these electrodes is much larger than the spacing between them, then the field near the center of the electrodes will have suitable geometry. However, many mass spectrometers require that there be a high magnetic field along the direction of the cylindrical axis which limits the spacing between the poles, i.e., pole gap, for creating such a high magnetic field. Therefore, the axial height of the cylindrical electrodes is limited by the small spacing between the poles of the permanent magnet for generating such a high magnetic field. Due to, at least in part, the limited axial height of such cylindrical electrodes, the electric field geometry near the top and bottom edges of the cylindrical electrodes is generally not the correct and desirable geometry. This is particularly the case when the electric field must be maintained at a particular ratio with the magnetic field in such mass spectrometers employing superimposed magnetic and electric fields.




In addition, mass spectrometers which employ superimposed magnetic and electric fields in an ion path assume that the magnetic field is perfectly homogenous within the boundaries of the magnet poles and zero outside those boundaries. However, it is virtually impossible to construct a magnet with this ideal field. In practice, there is always a fringing field which exists beyond the pole boundaries. Further, there is usually a significant inhomogeneity of the magnetic field inside the pole boundaries, unless a substantial cost is outlaid for producing a magnet which is substantially homogenous. For example, the field may vary within the pole boundaries in the range of about 10% of the average field therein. Due to such magnetic field inhomogeneity, resolution of mass spectrometers having superimposed magnetic and electric fields is significantly affected as the ratio of magnetic and electric fields is not consistently correct along the ion path.




SUMMARY OF THE INVENTION




There is a need in the art for improved mass spectrometer apparatus having superimposed magnetic and electric fields and methods regarding such spectrometer apparatus which reduce the effects of the problems described above. The present invention which may be compact and miniature in size compared to conventional spectrometers overcomes the problems described above and other problems as will become apparent to one skilled in the art from the detailed description below. Further, the mass spectrometer according to the present invention may be part of a portable analysis instrument, e.g., an in situ analysis device.




A double focusing mass spectrometer apparatus according to the present invention includes a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis with the first cylindrical sector electrode surface having an upper and lower edge and also includes a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis with the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode. An ion path is defined between the first and second cylindrical sector electrode surfaces. A first magnet pole and a second magnet pole are positioned proximate the upper and lower edges of the first and second cylindrical sector electrode surfaces, respectively, for providing a magnetic field in the ion path. A first array of electrodes is positioned between the upper edges of the first and second cylindrical sector surfaces and a second array of electrodes is positioned between the lower edges of the first and second cylindrical sector surfaces for use with the first and second cylindrical sector electrode surfaces to provide a desired electric field in the ion path perpendicular to the magnetic field.




In one embodiment of the apparatus, a ratio of a length of the first and second cylindrical sector electrode surfaces between the upper and lower edges in the direction of the cylindrical axis to the distance between the first and second cylindrical sector electrode surfaces is in the range of about 0.1 to about 1.5.




In another embodiment of the apparatus, the first array of electrodes includes at least two electrodes evenly spaced between the upper edges of the first and second cylindrical sector electrode surfaces. Further, the second array of electrodes includes at least two electrodes evenly spaced between the lower edges of the first and second cylindrical sector electrode surfaces. The embodiment of the apparatus further includes a voltage supply circuit for applying a predetermined voltage that varies logarithmically across the first and second array of electrodes.




In another embodiment of the apparatus, the first array of electrodes includes at least two electrodes logarithmically spaced between the upper edges of the first and second cylindrical sector electrode surfaces. Further, the second array of electrodes includes at least two electrodes logarithmically spaced between the lower edges of the first and second cylindrical sector electrode surfaces. This embodiment of the apparatus then includes a voltage supply circuit for applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the electrodes of the first and second electrode arrays, e.g., via a voltage divider network of equally valued resistors.




In yet another embodiment of the apparatus, the first and second arrays of electrodes are configured as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.




Another double focusing mass spectrometer apparatus according to the present invention includes two or more substrate portions positioned to define an ion path having superimposed magnetic and electric fields provided therein. A first substrate portion includes a first array of electrodes formed on one side thereof and a second substrate portion includes a second array of electrodes formed on a side thereof. The first and second arrays of electrodes are positioned generally parallel to one another for use in providing the electric field in the ion path. Further, the apparatus includes a first and second magnet pole located proximate the two or more substrate portions for providing the magnetic field in the ion path orthogonal to the electric field.




In one embodiment of the apparatus, a distance between the parallel first and second arrays of circular segment electrodes is less than about 0.1 times a radial dimension along which the parallel first and second circular segment electrode arrays are defined.




In a double focusing mass spectrometry method according to the present invention, the method includes providing a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis with the first cylindrical sector electrode surface having an upper and lower edge and includes providing a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis with the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode. An ion path is defined between the first and second cylindrical sector electrode surfaces. Thereafter, a magnetic field is generated in the ion path and a desired electric field is generated in the ion path perpendicular to the magnetic field using a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces, a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces, and the first and second cylindrical sector electrode surfaces.




In another method for use in double focusing mass spectrometer apparatus, the method includes providing a non-uniform magnetic field for an ion path of a double focusing mass spectrometer. An electrode assembly is formed to provide an electric field in the ion path. The forming of the electrode assembly includes forming two or more electrodes to a particular configuration as a function of the non-uniformity of the magnetic field such that the electric field in the entire ion path in the double focused mass spectrometer is at a predetermined ratio to the magnetic field.




In one embodiment of the method, forming the two or more electrodes includes configuring a first and second array of electrodes positioned generally parallel to one another as a function of the non-uniformity of the magnetic field, e.g., spacing and/or shaping electrodes of the first and second array of electrodes as a function of the non-uniformity of the magnetic field.




In yet another method of a double focusing mass spectrometry method according to the present invention, the method includes sealing two or more substrate portions together to define an ion path. A first substrate portion includes a first array of electrodes formed on a side thereof and a second substrate portion includes a second array of electrodes formed on a side thereof. The sealing of the two or more substrate portions together includes positioning the first and second arrays of electrodes generally parallel to one another. Thereafter, an electric field is generated in the ion path using at least the first and second arrays of electrodes. The electric field has a cylindrical geometry. Further, the method includes positioning a first and second magnet pole proximate the two or more substrate portions for providing a magnetic field in the ion path orthogonal to and superimposed with the electric field in the ion path.




The above summary of the present invention is not intended to describe each embodiment or every implementation of the present invention. Advantages, together with a more complete understanding of the invention, will become apparent and appreciated by referring to the following detailed description and claims taken in conjunction with the accompanying drawings.











BRIEF DESCRIPTION OF THE DRAWINGS





FIG. 1

is a graphical illustration generally showing an analyzer region for a double-focusing mass spectrometer including superimposed magnetic and electrical fields in an ion path according to the present invention.





FIG. 2

is one illustrative embodiment of a double-focusing mass spectrometer apparatus according to the present invention including an analyzer region as shown in FIG.


1


.





FIG. 3

is one embodiment of an electrode configuration for the analyzer region shown generally in FIG.


1


.





FIG. 4

is an alternate electrode configuration for the analyzer region shown generally in FIG.


1


.





FIG. 5

is another alternate electrode configuration for the analyzer region shown generally in FIG.


1


.





FIG. 6

is yet a further alternate electrode configuration for the analyzer region shown generally in

FIG. 1

employing techniques for compensating for an inhomogeneous magnetic field.





FIG. 7

is yet another alternate electrode configuration for the analyzer region shown generally in

FIG. 1

employing techniques for compensating for an inhomogeneous magnetic field.





FIG. 8

shows a top view of one illustrative embodiment of a double-focusing mass spectrometer apparatus according to the present invention.





FIG. 9

is a side view of the double-focusing mass spectrometer apparatus shown in FIG.


8


.





FIG. 10

is a cross-sectional view of the ion path shown in

FIG. 8

taken along line


10





10


thereof.





FIGS. 11A and 11B

are top and bottom views of one cylindrical electrode cap plate forming a portion of an electrode configuration for the double-focusing mass spectrometer apparatus of FIG.


8


.





FIG. 12A

is a side view of an alternate illustrative embodiment of a double-focusing mass spectrometer apparatus according to the present invention.





FIG. 12B

is a cross-sectional perspective view taken along lines


12


B—


12


B of the mass spectrometer apparatus of

FIG. 12A

showing an alternate construction technique for the double-focusing mass spectrometer apparatus according to the present invention.











DETAILED DESCRIPTION OF THE EMBODIMENTS




The present invention shall be generally described with reference to

FIGS. 1-2

. Thereafter, various embodiments of the present invention shall be described further with reference to

FIGS. 3-12

. It will become apparent to one skilled in the art that elements from one embodiment may be used in combination with elements of the other embodiments and that the present invention is not limited to the specific embodiments described herein but only as described in the accompanying claims.




The present invention is directed to a double-focusing mass spectrometer apparatus and methods regarding such an apparatus. Using one or more of the techniques or concepts described herein, a small, lightweight, and possibly battery-powered mass spectrometer apparatus may be constructed. For example, such a mass spectrometer may be hand-held and could be used for a wide variety of applications. Samples are preferably introduced in the gas phase, although it may also be possible to use the concepts described herein in a spectrometer wherein the samples are introduced in the liquid phase. Such a double-focusing mass spectrometer provides functionality in a mass range of about 1 (atomic mass unit) amu to about 200 amu with a resolution as low as 1 amu. Further, for example, the size of such a mass spectrometer is preferably about 100 cm


3


or less.




Generally, as shown in

FIG. 2

, the double-focusing mass spectrometer apparatus


50


includes an ion source or ionizer


54


for providing an ion beam and an analyzer region


10


, as shown in further detail in

FIG. 1

, wherein the trajectory of ionized atoms and molecules of the ion beam emerging from the ion source or ionizer


54


is influenced by the superimposed electrical and magnetic fields provided in ion path


21


. Once the ion beam is dispersed by the mass analyzer region


10


in its respective mass to charge ratios (m/e), the ions are collected and counted by an ion collector or detector


52


of the double-focusing mass spectrometer apparatus


50


. Subsequently, different electronic components and/or computer software give rise to the mass spectrum resulting from the collected ions as is known to those skilled in the art. The present invention focuses particularly on the analyzer region


10


of the double-focusing mass spectrometer apparatus


50


in which the superimposed magnetic and electrical fields are provided for influencing the trajectory of ionized atoms and molecules. As such, the ionizer


54


and the detector


52


may be any ionizer and/or detector generally used in double-focusing mass spectrometry or any other deflection-type mass spectrometry.




Various ionization methods are available and can be used. For example, the ionizer


54


may include electron impact ionization, chemical ionization, field desorption ionization, field ionization, fast atom bombardment, secondary ion bombardment, atmospheric pressure chemical ionization, electrospray ionization, and matrix-assisted desorption ionization. Preferably, particularly for gases, volatile compounds, and metallic vapors, electron impact ionization is used. Ion production by electron impact ionization, also known as electron bombardment ionization, generally, as shown in

FIG. 2

, involves the introduction of a sample into an ionization chamber


57


via a small aperture


56


. Generally, electrons are emitted typically using a filament and directed perpendicular to the trajectory of the neutral particles of the sample. Upon ionization, the ions are drawn out from inside the ionization chamber by an extractor electrode. The ions are then focused by additional electrodes and accelerated through the superimposed fields in the analyzer region


10


by an accelerating voltage (Va) applied by accelerating voltage (Va) source


55


. Further, a collimating slit, shown generally as


58


in

FIG. 2

, provides for entry of the ions into ion path


21


of analyzer region


10


.




Various components and electrode configurations may be used for providing such ionization, and the ionization is not limited to any particular ionizer configuration. For example, one or more field emission tip electrodes may be used for providing electrons as opposed to using a filament. Focusing is necessary to concentrate the beam into the small entrance to the analyzer region


10


as well as to minimize spread. Further, collimating is done by rejecting those ions that failed to focus due to large spread angles with the collimating slit


58


. This exit slit


58


also serves as the interface between the ionizer


54


and the analyzer region


10


. Both focusing and collimation of the ions are used for achieving a good resolution in the analyzer region


10


. Preferably, the ion source


54


provides z-focusing of the ions in the analyzer region


10


, e.g., such as by the ion source configuration and the applied accelerating voltage.




Once collimated, the ions enter an ion path


21


of the analyzer region


10


to be separated in their respective mass to charge ratios (m/e) as the electric field of the superimposed magnetic and electric fields is swept by application of a varying electrode voltage (Vd) applied to the electrode configuration


11


by sweep voltage source (Vd)


59


to generate the electric field of the superimposed fields. Any technique of sweeping the voltage may be used. For example, a sweep signal generator and a variable voltage source controlled thereby may be used. According to the present invention, double-focusing is used to provide for the separation of ions using a superimposed magnetic and electric field in the ion path wherein the magnetic force on the selected ion is double the electric force on the selected ion, and in the opposite direction, as further described below, preferably throughout the entire ion path


21


. As the electric field of the superimposed fields is swept and the magnetic field is kept fixed, the double focusing condition for ions having different m/e ratios will be satisfied so that detection is possible. Of course, the ratio of the voltage (Vd) applied for establishing the electric field strength and the accelerating voltage (Va) must be kept constant during the sweeping of the electric field.




Once the main ion beam, e.g., the collimated ions, is dispersed by the analyzer region


10


with respect to the mass to charge ratios (m/e), the ions are collected and counted by the ion detector


52


. There are many different ways to detect ions. For example, the detector


52


may be an electron multiplier such as a channel electron multiplier, an electrostatic focused electron multiplier, or a magnetic or cross-field electron multiplier. Further, the detector may be a scintillation/photo multiplier, faraday collectors, or ion to electron converters such as solid state detectors. In addition, such detectors may include microchannel plate detectors and ion sensitive emulsions. Various commercially-available detectors for such purposes may be used for providing ion detection.




For example, the detector may be a detection plate at which different charged masses will hit the detection plate and all ions will be collected at the same time. With such simultaneous detection, although the collection is more efficient, high demands are put on the electronics of the detector. If the detector is set to be fixed to only one particular position, the accelerating voltage for the ionizer


56


is varied to collect all the specific ions at the same detector position. Such a detector is generally illustrated in

FIG. 2

with detector slit


60


allowing for the ions at a particular position to be detected. One skilled in the art will recognize that any particular detector


52


may be used for ion detection. For example, several commercially-available detectors include microchannel plates (MCP), channeltrons, and microsphere plates (MSP).




The analyzer region


10


according to the present invention for the double-focusing mass spectrometer


50


is partially illustrated in FIG.


2


and further illustrated graphically in FIG.


1


. Generally, the analyzer region


10


is provided with superimposed magnetic and electric fields in the ion path


21


of the analyzer region


10


. Further, generally, according to the present invention, the electric field has a cylindrical geometry and is proportional to 1/r, where r is the radial distance associated with the cylindrical geometry. In other words, a generally radial electric field of cylindrical geometry is generated in the ion path


21


by an electrode configuration


11


, e.g., the electric field intensity along a circumferential line


20


described by r in the z=0 plane is constant. Further, the equipotential lines within the ion path


21


would run substantially parallel to the z axis, while the electric field lines would generally be radial in x-y planes along the z axis in the ion path


21


. Perpendicular to the radial electric field in the ion path


21


is the magnetic field which is generally parallel with the z axis.




The analyzer region


10


includes the electrode configuration


11


for use in providing the electric field of cylindrical geometry in the ion path


21


. Generally, the electrode configuration


11


includes a first cylindrical sector electrode


12


and a second cylindrical sector electrode


14


. Each of the two cylindrical sector electrodes


12


,


14


have the same cylinder axis


15


extending through origin (


0


) but have different radii. In other words, the first cylindrical sector electrode


12


includes an inner surface


22


facing inward towards ion path


21


having a radius (r


b


), and second cylindrical sector electrode


14


includes an inner surface


24


facing inward towards ion path


21


having a second radius (r


a


). In other words, the cylindrical sector electrode surfaces


22


,


24


are disposed in opposing relationship with one another. The ion path


21


is defined between the opposing cylindrical sector electrode surfaces


22


,


24


. In general, the electric field is provided by providing an electrical potential between the first cylindrical sector electrode


12


and second cylindrical sector electrode


14


such that the electrical potential between the electrodes is proportional to log(r).




The analyzer region


10


of the double-focusing mass spectrometer


50


according to the present invention employs the cylindrical geometry for the radial electric field (∈), i.e., a field inversely proportional to r, and a magnetic field (B) perpendicular to the electric field, i.e., parallel to the z axis. The polarity of the electric and magnetic fields can be chosen such that the forces from the electric and magnetic fields are anti-parallel. If F is the net force on an ion in the ion path


21


, v is the component of ion velocity in the plane of deflection, and q is the ionic charge, then








F=qBv−q∈.








Here a radial positive force is inward and a negative force is outward along the radius of curvature of an ion trajectory through the ion path. The radius of curvature r and its dispersion can then be expressed by







r
=


mv
2


qBv
-




,




and







r

r

=


(


Bv
-

2

ε



Bv
-
ε


)






v

v

.












Thus, a special case of double-focusing is provided, i.e., zero dispersion of r with respect to v, when the magnetic force (qvB) is just twice the electric force (q∈)








Bv=


2∈.






For an object and image at the entrance and exit of the field boundaries, respectively, this special case design yields direction-focusing at a deflection angle of π/{square root over (2)}(127.3°), exactly like a cylindrical electrostatic energy analyzer. In other words, the cylindrical sectors in such a design would be 127.3° sectors. Sectors of other angular configurations are possible. For example, in a more convenient 90° deflection angle shown in the embodiments illustrated herein, e.g., the apparatus shown in

FIG. 8

, the object and image foci are located at about 0.35r from the field boundaries. If (E) is the ion kinetic energy, the mass selected is given by







m
=



q
2



B
2



r
2



8

E



,










which may be compared with






m
=



q
2



B
2



r
2



2

E












for a simple magnetic sector (no electric field).




Therefore, desirable performance of the analyzer region


10


depends particularly on having the correct ratio of electric to magnetic fields at each point along the ion path


21


. As a result, a proper bending radius or a radius of curvature is effected.




Generally, the magnetic field parallel to the z axis and orthogonal to the electric field in the ion path


21


is provided by yoke and pole assembly


40


, as shown generally in

FIG. 2

, including first magnetic pole


16


and second magnetic pole


18


as shown in FIG.


1


. The magnetic field preferably has a strength that is as high as possible. For example, the magnetic field strength may be in the range of about 1 T to about 2 T or even higher (referred to hereinafter as a high magnetic field). The permanent magnet has a pole gap preferably of about 1 mm to about 5 mm to provide such a high magnetic field in the ion path


21


of the analyzer region


10


. For example, such high magnetic field may be provided by high energy-product NdFeB poles used with an iron yoke in the yoke and pole assembly


40


. However, one skilled in the art will recognize that the magnetic field may be provided by any suitable permanent magnet, electromagnet, etc.




As described above, the performance of the double-focusing mass spectrometer apparatus


50


, and particularly the analyzer region


10


, depends on having the correct ratio of electric to magnetic field intensities at each point along the ion path


21


. If the axial height along the z axis of the cylindrical sector electrodes


12


,


14


is much larger than the spacing between them (i.e., r


b


−r


a


), then the field near the center of the electrodes


12


,


14


(generally represented by circumferential line


20


extending through ion path


21


) would provide such a correct ratio of electric to magnetic field intensities. However, the analyzer region


10


preferably requires that there be a high magnetic field parallel to the cylindrical axis (i.e., z axis). A high magnetic field enhances performance by making the ion energy higher for each selected mass (i.e., E is proportional to B


2


), thereby making space charge and surface charge effects on the ion trajectories less important. As such, the spacing between the poles (i.e., pole gap) of the magnet is small. Therefore, the axial height along the z axis of the first and second cylindrical sector electrodes


12


,


14


is limited by the small spacing between the poles


16


,


18


of a permanent magnet used to provide such a high magnetic field. In other words, the axial height of the first cylindrical sector electrode


12


and the second cylindrical sector electrode


14


is limited by the magnet pole spacing. The axial height of the first cylindrical sector electrode


12


extends from a lower edge


34


to an upper edge


32


of the electrode


12


along the z axis. Likewise, the axial height of the second cylindrical sector electrode


14


extends from a lower edge


38


to upper edge


36


along the z axis. Due to the limited axial height of the electrodes


12


,


14


, the correct electric field for providing the desired ratio between electric and magnetic field intensities near the upper and lower edges of the cylindrical sector electrodes


12


,


14


is not assured with use of just the electrodes


12


,


14


alone.




To provide for a correct “fringing” field near the upper edges


32


,


36


of the first and second cylindrical sector electrodes


12


,


14


, respectively, and near the lower edges


34


,


38


of the first cylindrical and second cylindrical sector electrodes


12


,


14


, respectively, the electrode configuration


11


further includes arrays of intermediate electrodes


26


,


28


. With use of the arrays of intermediate electrodes


26


,


28


, the correct ratio of magnetic and electric field intensities is attained even with the axial height limitations resulting from the small magnetic pole spacing. As used herein, a fringing field refers to a magnetic or electric field which deviates from the ideal proximate to and/or outside the geometrical boundaries of the electrode configuration


11


and magnetic pole assembly. The arrays of intermediate electrodes


26


,


28


allows the magnetic pole spacing to be reduced. Preferably, according to the present invention, the ratio of the axial height of the first and second cylindrical sector electrodes


12


,


14


between the upper edges


32


,


36


and lower edges


34


,


38


to the radial distance between the first and second cylindrical sector electrodes


12


,


14


is in the range of about 0.1 to 1.5. However, the ratio of the axial height of the first and second cylindrical sector electrodes


12


,


14


to the radial distance between the first and second cylindrical sector electrodes may be greater than 1.5.




As shown in

FIG. 1

, the intermediate electrodes include a first electrode array


26


positioned between the upper edge


32


of first cylindrical sector electrode


12


and the upper edge


36


of the second cylindrical sector electrode


14


. Likewise, a second electrode array


28


is positioned between the lower edges


34


,


38


of the first and second cylindrical sector electrodes


12


,


14


. In one embodiment, as shown in

FIG. 1

, each of the arrays


26


,


28


include a plurality of circular segment electrodes having different radii and spaced between the first and second cylindrical sector electrodes


12


,


14


. In other words, each of the segment electrodes of the first and second electrode arrays


26


,


28


are circular segments with the same axis as the first and second cylindrical sector electrodes


12


,


14


and which all generally have the same radial cross sectional dimensions. However, it will be recognized from the description herein as further described below that the shape of the intermediate electrodes may vary.




Generally, each of these circular segment electrodes has a voltage applied thereto that is equal to the voltage which would exist at the same value of r if the first and second cylindrical sector electrodes


12


,


14


were infinite in height. Application of the appropriate voltages in the configuration of the first and second electrode arrays


26


,


28


to assure correct electric field geometry near the upper and lower edges of the first and second cylindrical sector electrodes


12


,


14


is illustratively shown in the embodiments of

FIGS. 3 and 4

.





FIG. 3

shows one embodiment of an electrode configuration


100


positioned between magnet poles


16


,


18


for assuring a correct electric field geometry throughout the ion path


101


. The electrode configuration


100


includes first and second cylindrical sector electrodes


106


,


108


substantially like those shown in FIG.


1


. First and second electrode arrays


110


,


112


of circular segment electrodes are provided to achieve the correct fringing field near the upper and lower edges of the first and second cylindrical sector electrodes


106


,


108


. The first electrode array


110


includes a predetermined number of circular segment electrodes evenly spaced between the upper edges


121


,


123


of the first and second cylindrical sector electrodes


108


,


106


. Likewise, the second array of electrodes


112


includes the same predetermined number of circular segment electrodes evenly spaced between the lower edges


125


,


127


of the first and second cylindrical sector electrodes


108


,


106


. Voltage supply


118


applies a predetermined voltage (Vd) to each of the electrodes of the first and second electrode arrays


110


,


112


. The predetermined voltages applied to the electrodes vary logarithmically across the first and second array of electrodes


110


,


112


at a particular point in time. Such logarithmic varying voltages are applied by using logarithmically varying resistors of a resistor network


114


which forms a voltage divider network with voltage supply


118


for applying the logarithmically varying predetermined voltages to the electrodes of the first array of electrodes


110


. Likewise, a resistor network


116


forms a voltage divider network with voltage supply


118


for applying logarithmically varying voltages to the electrodes of the second array of electrodes


112


.





FIG. 4

shows an alternate way of achieving the same fields as achieved with the electrode configuration and voltage divider networks shown in FIG.


3


. The electrode configuration


130


as shown in

FIG. 4

includes an electrode array


136


including a predetermined number of circular segment electrodes which are spaced logarithmically in radius. In other words, the gaps d


1


-d


4


are sized to space the circular segment electrodes of the array


136


between first and second cylindrical sector electrodes


132


,


134


in a logarithmic manner. In combination with such logarithmic spacing of the electrodes of the array of electrodes


136


, the resistors of resister network


138


connected between the electrodes are of equal resistance values, unlike the configuration of

FIG. 3

where such resistance values varied logarithmically. The voltage supply


140


in combination with the resistor network


138


form a voltage divider network which applies the appropriate voltages to the first and second cylindrical sector electrodes


132


,


134


and the array of electrodes


136


.





FIG. 5

shows yet another alternate electrode configuration


160


for achieving a correct electric field geometry such that the ratio of the electric to magnetic field forces at each point along the ion path is attained. Electrode configuration


160


includes at least a first and second array of electrodes


170


,


172


positioned between magnetic poles


162


,


164


. If the first and second arrays of electrodes


170


,


172


are extended over a radial range of r which is much larger than the axial height (h) of the electric field, and also therefore much larger than the magnet pole gap, the electrode configuration


160


may only optionally require first and second cylindrical sector electrodes


166


,


168


which form the radial boundaries of the electric field. For example, if the cylindrical sector electrodes


166


,


168


which form the radial boundaries of the electric field are sufficiently far away from the paths taken by the ions in the analyzer region, then their influence on the field experienced by the ions is small, and one or both of the cylindrical sector electrodes


166


,


168


may be eliminated from the electrode configuration


160


. As such, the electric field superimposed with the magnetic field may be completely provided with the use of two electrode arrays


170


,


172


generally parallel to one another and which extend over a range of r that is much larger than the axial height of the magnet gap between poles


162


,


164


. Preferably, the electrode arrays extend over a range of r that is at least about 10 times the magnet gap to eliminate the use of one or more of the cylindrical sector electrodes. If the cylindrical sector electrodes


166


,


168


are not used, then the potentials applied to the innermost electrodes


176


and the outermost electrodes


174


of the first and second electrode arrays


170


,


172


can be adjusted to minimize the deviation from ideality of the electric field along the ion path. For example, the potentials applied to the outer electrodes can be increased to minimize the deviations from a log(r) potential in the region of the ion trajectory.




The ideal fields for the double-focusing mass spectrometer apparatus


50


include the cylindrical geometry for the electric field and a magnetic field which is perfectly homogenous within the boundaries of the magnet poles and zero outside those boundaries. As previously described in the Background of the Invention section herein, it is virtually impossible to construct a magnet with this ideal homogenous magnetic field. In practice, there is always a magnetic fringing field which extends beyond the pole boundaries, and the magnetic field inside the pole boundaries is usually significantly inhomogeneous. For example, inside the pole boundaries, the magnetic field at one position may vary by 10% from the magnetic field at another position.




The optimum performance of the analyzer region


10


depends particularly on having the correct ratio of electric to magnetic fields at each point along the ion path


21


. Such inhomogeneity in the magnetic field must be corrected to maintain the optimum ratio of the electrical and magnetic fields superimposed in the ion path


21


. In accordance with an electric and magnetic fringing field correction process according to the present invention, it is possible to shape the electric field in a manner which deviates from the ideal cylindrical geometry such that it matches the deviation from the ideality of the magnetic field due to its inhomogeneity so as to maintain the optimum ratio of the superimposed magnetic and electric fields. Such a correction process is initiated with the design and construction of the magnet providing the magnetic field. After the magnet is designed and constructed, the magnetic field generated by the constructed magnet may be measured and mapped. The magnetic field measurement and mapping involves measuring the distribution of the magnetic field along the coordinates typical for ion trajectory through the analyzer region


10


. Such a magnetic field distribution defines the desired electric field as the electric field is at a particular ratio with respect to the magnetic field. For example, the magnetic field of a magnet design may provide a magnetic field that is larger at the center region of the magnet pole as opposed to the edges. This would then require a larger electric field in this center region. The electric field at each point in the ion trajectory should be given by the equation






ε
=



(

B


(

E

2

m


)


)


1
2


.











After the magnetic field is measured and mapped, the fringing field correction electrodes, e.g., first and second electrode arrays


26


,


28


, are designed using finite element simulation. In this process, the electrode shapes and/or positions are adjusted empirically. Then a numerical calculation of the three-dimensional field distribution is performed. Adjustments are then made until the electric field along the ion path (ξ) is suitably approximated by the expression







ε


(
ξ
)


=


B


(
ξ
)






(

E

2

m


)


1
2


.












For example, the first and second arrays of electrodes


26


,


28


are configured such that the electric field matches the deviation from the ideality of the magnetic field so as to maintain the appropriate ratio of the electric field to magnetic field in the ion path


21


as desired. Although, preferably, according to the present invention, the electrode structure is configured to provide the appropriate ratio, one skilled in the art from the description herein will recognize that the magnetic pole structure, the electrode structure, or a combination thereof, may be configured to provide the appropriate ratio.





FIGS. 6 and 7

show two illustrative embodiments of alternate electrode configurations


200


,


230


, respectively. Each electrode configuration is adjusted to give the optimum approximation to the desired electric field for matching the deviation from ideality of the magnetic field provided by the magnet poles. As shown in

FIG. 6

, the electrode configuration


200


includes first and second cylindrical sector electrodes


206


,


208


positioned between magnet poles


202


,


204


. Further, the electrode configuration


200


includes first and second arrays of circular segment electrodes


210


,


212


. First electrode array


210


is positioned between the upper edges


211


,


213


of first and second cylindrical sector electrodes


208


,


206


, respectively. Likewise, second electrode array


212


is positioned between the lower edges


217


,


219


of first and second cylindrical sector electrodes


208


,


206


, respectively.




Each of the first and second arrays of electrodes


210


,


212


include a predetermined number of circular segment electrodes which are spaced to give the optimum approximation to the desired electric field to match the deviation from ideality of the magnetic field. For example, as shown in

FIG. 6

, in a typical case where the magnetic field is larger at the center of the magnet poles, the spacing of the circular segment electrodes in the arrays


210


,


212


will be smaller in the center region as represented by gaps DLL as opposed to the spacing towards the other regions of the ion path


201


as represented by the larger gaps d


2


, d


3


. As such, a correspondingly larger electric field is provided in the center region to match the magnetic field which is larger at the center of the magnet poles. Therefore, the desired ratio of the magnetic field to the electric field is accomplished. Further, as shown in

FIG. 6

, the first and second electrode arrays


210


,


212


have the appropriate voltages applied thereto by the voltage divider network including voltage supply


218


and resistor networks


216


,


214


in a like manner to that previously described herein.




As shown in the embodiment of

FIG. 7

, the adjustment of the electric field may be accomplished by formation of electrode sectors


236


-


239


positioned between first and second cylindrical sector electrodes


232


,


234


. Appropriate voltages V


1


-V


4


may be applied to such electrode sectors to provide an electric field of the appropriate ratio to the magnetic field. This embodiment allows the required relationship between ∈ and B to be fulfilled piecewise, sector by sector.




One skilled in the art will recognize that the first and second arrays of electrodes


26


,


28


positioned between the upper edges


32


,


36


and lower edges


34


,


38


of the first and second cylindrical sector electrodes


12


,


14


as shown in

FIG. 1

may take the form of various configurations in providing a desired electric field to provide the correct ratio of electric to magnetic fields in compensating for inhomogeneity of the magnet poles. For example, the size, the position, the shape, the spacing, and/or any other suitable characteristic of the electrodes may be adjusted to provide the appropriate electric field. As such, the present invention is not limited to any particular configuration of the intermediate electrodes of the first and second electrode arrays


26


,


28


, but is limited only according to the scope of the appended claims. For example, as shown by the dashed line electrode ends


233


,


235


in

FIG. 7

, the electrode arrays may include electrode segments which are not parallel to one another, and are not circular in shape. Such shaping of the electrodes of the arrays may be beneficial, for example, in the attainment of the desired electric field at the ends of the analyzer region.




This method of establishing the electric field geometry matching the deviation of the magnetic field such that a correct ratio is maintained in the ion path


21


of the analyzer region


10


may be accomplished effectively via the use of electrodes which are lithographically deposited on substrates. By lithographically depositing such electrodes on substrates for use in defining the electric field, tailoring of the electrodes in order to tailor the electric field to match the field of the inhomogeneous magnet may be readily accomplished. The use of electrodes lithographically deposited on substrates, e.g., ceramic substrates, shall be described further with regard to the double-focusing mass spectrometer apparatus


300


shown and described with reference to

FIGS. 8-11

.





FIG. 8

shows one illustrative embodiment of a double-focusing mass spectrometer apparatus


300


according to the present invention.

FIG. 9

is a side view of the mass spectrometer apparatus


300


. The double-focusing mass spectrometer apparatus


300


includes an ion source


302


for providing ions into an ion path


307


defined in an analyzer region


306


. The trajectory of the ions is effected in the analyzer region


306


by superimposed magnetic and electric fields in the ion path


307


with the output provided to a detector


304


.

FIG. 8

is a top view of the double-focusing mass spectrometer apparatus


300


with a yoke and magnet pole


370


for providing the magnetic field shown in dashed line.




Preferably, the ion source


302


is an electron impact ionizer with a slit geometry, e.g., a slit geometry refers to an ion aperture which is made in the radial dimension (r). The electron impact ionizer includes a tungsten hairpin filament emitter


319


operably connected to filament electrodes


318


. The ion source


302


further includes anode


320


, extractor electrode


321


, and focus electrode


323


all aligned for providing ions through object slit


322


. Further, the ion source


302


includes an electron collector


325


for monitoring the ionizing electron current applied to the ionizer.




The components of the ion source


302


are connected together with suitable insulative portions


324


positioned as required. The ion source


302


is mounted on an L-shaped frame


308


by mounting hardware


316


. The ion source


302


is mounted such that it is sealed with ion path


307


to provide an airtight throughway from the ion source


302


to the analyzer region


306


.




The detector


304


is preferably a commercially-available detector such as a Galileo multi-channel plate available under the trade designation


1333


-


1200


, e.g., a microchannel plate having a thickness of about 1.1 mm and a gain of approximately 10


5


. However, any suitable detector may be used.




The magnet


370


may include an iron yoke mounting high energy-product NdFeB poles. For example, the magnet may have a pole gap of about 4 mm to provide a magnetic flux density of approximately 1 T. The detector


304


detects the ions through slit


326


.




As described previously herein, the focus of the present invention is with respect to the analyzer region


306


of the double-focusing mass spectrometer apparatus


300


. The analyzer region


306


is mounted with respect to the L-shaped frame


308


by mounting hardware


312


and is insulated from the L-shaped frame


308


by insulated regions


310


.




The analyzer region


306


includes an outer electrode portion


340


A and an inner electrode portion


340


B. Outer electrode portion


340


A includes an outer cylindrical sector electrode surface


341


A defining a first radial distance from a cylindrical axis and the inner electrode portion


340


B includes a second cylindrical sector electrode surface


341


B defining a second radial distance from the same cylindrical axis. The cylindrical sector electrode surfaces


341


A and


341


B define the ion path


307


therebetween.





FIG. 10

is a cross-section view taken at line


10





10


of FIG.


8


.

FIG. 10

provides a more detailed view of the analyzer region


306


. As shown in

FIG. 10

, in addition to the outer and inner electrode portions


340


A and


340


B, the analyzer region


306


includes a first cylindrical electrode cap plate


344


and a second cylindrical electrode cap plate


348


. The first and second cylindrical electrode cap plates


344


,


348


sandwich the outer and inner electrode portions


340


A and


340


B to further define the ion path


307


.




Desired configurations of electrode arrays


350


,


352


are lithographically deposited on first and second cylindrical electrode cap plates


344


,


348


, respectively. As shown in

FIG. 10

, each electrode array


350


,


352


includes nine intermediate electrodes deposited between first and second cylindrical electrode surfaces


341


A,


341


B. For example, electrode array


350


includes nine intermediate electrodes deposited on surface


383


between upper edges


374


,


372


of electrode surfaces


341


A,


341


B while electrode array


352


includes nine intermediate electrodes deposited on surface


385


between the lower edges


378


,


376


of electrode surfaces


341


A,


341


B. As used herein, depositing electrodes on a surface includes depositing by chemical vapor deposition processes, screen printing, vacuum evaporation, sputtering, or any other method of forming the electrodes on the substrate as opposed to attaching a discrete part to the substrate.




The electrode cap plates


344


,


348


may be formed of any insulative substrate material, preferably ceramic materials. The electrode array


350


,


352


may be any conductive material, e.g., copper or other metal, graphite, doped semiconductor or superconductor materials formed on the substrate material. Further, the inner and outer electrode portions


340


A,


340


B may be formed of a copper alloy or any other appropriate metal.




As shown in

FIGS. 10 and 11

, the circular segment electrodes of the electrode arrays


350


,


352


are connected to each other via a resistor string which may also be deposited lithographically on the opposite surface of the cap plates


344


,


348


on which the electrode arrays


350


,


352


are deposited so as to establish the correct voltages applied to the electrodes of the electrode array


350


,


352


. For example, the intermediate electrode


5


of electrode array


350


is connected through a conductor filled via


354


to a resister pad


358


on the outer surface


382


of cap plate


344


. Likewise, intermediate electrode


5


of electrode array


352


is connected to resister pad


360


by conductor filled via


356


through cap plate


348


. Using such construction techniques, any of the electrode configurations, particularly the electrode array configurations as described herein, may be produced using lithographic processing, particularly lithographic deposition of electrodes and resistors. This is particularly beneficial when such configurations require fine line widths between electrodes.





FIG. 11A

further shows in detail first cylindrical electrode cap plate


344


, which is substantially similar to cap plate


348


.

FIG. 11A

is a bottom view of the cap plate


344


which shows the inner surface


383


having an inner electrode


362


and an outer electrode


364


along with the electrode array


350


lithographically deposited thereon. The inner and outer electrodes


362


,


364


when assembled with inner and outer electrode portions


340


A and


340


B are in direct contact with such portions


340


A,


340


B. As shown, the array of electrodes


350


include circular segment electrodes, all of different radii but of substantially the same line width. Further, the vias for connection to the opposite side of the electrode cap plate


344


are shown by the reference numerals


385


with via


354


as shown in

FIG. 10

numbered differently.





FIG. 11B

is a top view of first cylindrical electrode cap plate


344


showing the outer surface


382


on which a lithographically deposited resister string R


1


-R


10


is deposited. For example, as shown in

FIGS. 8-11

, an electrode configuration very similar to that illustratively shown in

FIG. 3

is provided. For example, the intermediate electrodes of the electrode arrays


350


,


352


are equally spaced between the inner and outer electrode surfaces


341


A,


341


B. Further, as shown in

FIG. 11B

, the resistors R


1


-R


10


vary logarithmically across the intermediate electrodes of the electrode array


350


. In other words, R


1


which connects the inner electrode


362


to intermediate electrode


1


, R


2


which connects the intermediate electrode


1


and intermediate electrode


2


of electrode array


350


, and R


3


which is connected between intermediate electrode


2


and intermediate electrode


3


of the electrode array


350


vary logarithmically.





FIGS. 12A and 12B

illustrate an additional embodiment of a double-focusing mass spectrometer apparatus


400


according to the present invention.

FIG. 12A

is a side view of the mass spectrometer apparatus


400


with

FIG. 12B

being a cross-sectional view along line


12


B—


12


B as shown in FIG.


12


A.

FIGS. 12A and 12B

illustrate a fabrication method for a mass spectrometer apparatus according to the present invention.




The mass spectrometer apparatus


400


includes an ionizer


402


, a detector


403


, and an analyzer region


404


all formed together in a simplified process. As shown in

FIG. 12A

, the mass spectrometer apparatus


400


is formed of multiple layers of ceramic plates. For example, in

FIG. 12A

the various layers include


408


-


415


. Each of the layers is provided separately and hermetically sealed to one another by glass solder joints.




A portion of the mass spectrometer apparatus


400


is shown in

FIG. 12B

in the cross-sectional view along line


12


B—


12


B of

FIG. 12A

to generally illustrate the fabrication process. This perspective view shows that each of the ceramic layers


408


-


415


can have various layers formed thereon. For example, ceramic layer


408


may include an electrode array


412


lithographically deposited thereon. In addition, discrete components may be used with the ceramic layers, although it is preferred to fabricate electrode arrays by lithographic deposition techniques.




One skilled in the art will recognize that any of the electrode configurations described herein or combinations thereof may be formed in the manner as described with regard to

FIGS. 12A and 12B

. Further, other fabrication techniques may be utilized to provide a double-focusing mass spectrometer apparatus according to the present invention as described herein. The present invention is not limited to one particular fabrication technique.




All patents and references disclosed herein are incorporated by reference in their entirety, as if individually incorporated. Further, although the present invention has been described with particular reference to various embodiments thereof, variations and modifications of the present invention can be made within the contemplated scope of the following claims, as is readily known to one skilled in the art.



Claims
  • 1. A double-focusing mass spectrometer apparatus comprising:a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis, the first cylindrical sector electrode surface having an upper and lower edge; a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis, the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; a first magnet pole and a second magnet pole positioned proximate the upper and lower edges of the first and second cylindrical sector electrode surfaces, respectively, for providing a magnetic field in the ion path; and a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces and a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces for use with the first and second cylindrical sector electrode surfaces to provide a desired electric field in the ion path perpendicular to the magnetic field, wherein the first and second arrays of electrodes are configured as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path such that mass selection using the mass spectrometer is achieved independent of ion velocity.
  • 2. The apparatus of claim 1, wherein a ratio of a length of the first and second cylindrical sector electrode surfaces between the upper and lower edges in the direction of the cylindrical axis to the distance between the first and second cylindrical sector electrode surfaces is in the range of about 0.1 to 1.5
  • 3. A double-focusing mass spectrometer apparatus comprising:a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis, the first cylindrical sector electrode surface having an upper and lower edge; a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis, the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; a first magnet pole and a second magnet pole positioned proximate the upper and lower edges of the first and second cylindrical sector electrode surfaces, respectively, for providing a magnetic field in the ion path; a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces and a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces for use with the first and second cylindrical sector electrode surfaces to provide a desired electric field in the ion path perpendicular to the magnetic field, wherein the first array of electrodes includes at least two electrodes evenly spaced between the upper edges of the first and second cylindrical sector electrode surfaces, and further wherein the second array of electrodes includes at least two electrodes evenly spaced between the lower edges of the first and second cylindrical sector electrode surfaces; and a voltage supply circuit for applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the electrodes of the first and second electrode arrays, wherein the predetermined voltage applied varies logarithmically across the first and second array of electrodes.
  • 4. The apparatus of claim 3, wherein the voltage supply circuit includes a voltage divider network of logarithmically varying resistors.
  • 5. A double-focusing mass spectrometer apparatus comprising:a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis, the first cylindrical sector electrode surface having an upper and lower edge; a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis, the second cylindrical sector electrode having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; a first magnet pole and a second magnet pole positioned proximate the upper and lower edges of the first and second cylindrical sector electrode surfaces, respectively, for providing a magnetic field in the ion path; and a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces and a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces for use with the first and second cylindrical sector electrode surfaces to provide a desired electric field in the ion path perpendicular to the magnetic field, wherein the first array of electrodes includes at least two electrodes logarithmically spaced between the upper edges of the first and second cylindrical sector electrode surfaces, and further wherein the second array of electrodes includes at least two electrodes logarithmically spaced between the lower edges of the first and second cylindrical sector electrode surfaces.
  • 6. The apparatus of claim 5, wherein the apparatus further includes a voltage supply circuit for applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the electrodes of the first and second electrode arrays.
  • 7. The apparatus of claim 6, wherein the voltage supply circuit includes a voltage divider network of equally valued resistors.
  • 8. The apparatus of claim 1, wherein the first and second arrays of electrodes are spaced as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 9. The apparatus of claim 1, wherein the first and second arrays of electrodes are shaped as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 10. A double-focusing mass spectrometer apparatus comprising:two or more substrate portions positioned to define an ion path having superimposed magnetic and electric fields provided therein, wherein a first substrate portion includes a first array of electrodes formed on one side thereof defined radially from an axis and wherein a second substrate portion includes a second array of electrodes formed on a side thereof defined radially from the axis, the first and second arrays of electrodes are positioned generally parallel to one another for use in providing the electric field in the ion path; and a first and second magnet pole located proximate the two or more substrate portions for providing the magnetic field in the ion path orthogonal to the electric field, wherein a radial distance along which the first and second array of electrodes are defined is greater than about 10 times a distance in the direction of the axis between the parallel first and second arrays of electrodes.
  • 11. The apparatus of claim 10, wherein the first and second arrays of electrodes are first and second arrays of circular segment electrodes.
  • 12. The apparatus of claim 11, wherein the apparatus further includes:a first cylindrical sector electrode surface defined at a first radial distance from the axis, the first cylindrical sector electrode surface having an upper and lower edge; and a second cylindrical sector electrode surface defined at a second radial distance from the axis, the second cylindrical sector electrode surface having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode surface, the ion path defined between the first and second cylindrical sector electrode surfaces, wherein the first array of circular segment electrodes is positioned between the upper edges of the first and second cylindrical sector surfaces and the second array of circular segment electrodes is positioned between the lower edges of the first and second cylindrical sector surfaces for use in providing the electric field in the ion path.
  • 13. The apparatus of claim 12, wherein the first array of circular segment electrodes includes at least two circular segment electrodes evenly spaced between the upper edges of the first and second cylindrical sector electrode surfaces, and further wherein the second array of circular segment electrodes includes at least two circular segment electrodes evenly spaced between the lower edges of the first and second cylindrical sector electrode surfaces.
  • 14. The apparatus of claim 13, wherein the apparatus further includes a voltage supply circuit for applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the circular segment electrodes of the first and second electrode arrays.
  • 15. The apparatus of claim 14, wherein the voltage supply circuit includes a first resistor network formed on a side of the first substrate portion opposite the first array of electrodes and a second resistor network formed on a side of the second substrate portion opposite the second array of electrodes.
  • 16. The apparatus of claim 14, wherein the predetermined voltage applied varies logarithmically across the first and second array of electrodes.
  • 17. The apparatus of claim 14, wherein the voltage supply circuit includes a voltage divider network of logarithmically varying resistors.
  • 18. The apparatus of claim 12, wherein the first array of circular segment electrodes includes at least two circular segment electrodes logarithmically spaced between the upper edges of the first and second cylindrical sector electrode surfaces, and further wherein the second array of circular segment electrodes includes at least two circular segment electrodes logarithmically spaced between the lower edges of the first and second cylindrical sector electrode surfaces.
  • 19. The apparatus of claim 18, wherein the apparatus further includes a voltage supply circuit for applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the circular segment electrodes of the first and second electrode arrays.
  • 20. The apparatus of claim 19, wherein the voltage supply circuit includes a first resistor network formed on a side of the first substrate portion opposite the first array of electrodes and a second resistor network formed on a side of the second substrate portion opposite the second array of electrodes.
  • 21. The apparatus of claim 19, wherein the voltage supply circuit includes a voltage divider network of equally valued resistors connected across each of the first and second arrays of electrodes.
  • 22. A double-focusing mass spectrometer apparatus comprising:two or more substrate portions positioned to define an ion path having superimposed magnetic and electric fields provided therein, wherein a first substrate portion includes a first array of electrodes formed on one side thereof defined radially from an axis and wherein a second substrate portion includes a second array of electrodes formed on a side thereof defined radially from the axis, the first and second arrays of electrodes are positioned generally parallel to one another for use in providing the electric field in the ion path; and a first and second magnet pole located proximate the two or more substrate portions for providing the magnetic field in the ion path orthogonal to the electric field, wherein the first and second arrays of electrodes are configured as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path such that mass selection using the mass spectrometer is achieved independent of ion velocity.
  • 23. The apparatus of claim 22, wherein the first and second arrays of electrodes are spaced as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 24. The apparatus of claim 22, wherein the first and second arrays of electrodes are shaped as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 25. The apparatus of claim 22, wherein the first and second arrays of electrodes are deposited on a surface of ceramic substrates.
  • 26. A double-focusing mass spectrometry method, the method comprising:providing a first cylindrical sector electrode surface defined at a first radial distance from an axis, wherein the first cylindrical sector electrode surface has an upper and lower edge; providing a second cylindrical sector electrode surface defined at a second radial distance from the axis, wherein the second cylindrical sector electrode has an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, and further wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; generating a magnetic field in the ion path; and generating a desired electric field in the ion path perpendicular to the magnetic field using a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces, a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces, and the first and second cylindrical sector electrode surfaces, wherein the first array of electrodes includes at least two circular segment electrodes evenly spaced between the upper edges of the first and second cylindrical sector electrode surfaces, wherein the second array of electrodes includes at least two circular segment electrodes evenly spaced between the lower edges of the first and second cylindrical sector electrode surfaces, and further wherein generating the desired electric field in the ion path perpendicular to the magnetic field includes: applying a voltage to each of the electrodes of the first array of electrodes, wherein the voltages applied to the first array of electrodes vary logarithmically from electrode to electrode from the first cylindrical sector electrode surface across the first array of electrodes to the second cylindrical sector electrode surface, and applying a voltage to each of the electrodes of the second array of electrodes, wherein the voltages applied to the second array of electrodes vary logarithmically from electrode to electrode from the first cylindrical sector electrode surface across the second array of electrodes to the second cylindrical sector electrode surface.
  • 27. The method of claim 26, wherein applying the voltage to each electrode of the first and second arrays of electrodes includes connecting a logarithmically varying resistor network across each of the first and second electrode arrays.
  • 28. A double-focusing mass spectrometry method, the method comprising:providing a first cylindrical sector electrode surface defined at a first radial distance from an axis, wherein the first cylindrical sector electrode surface has an upper and lower edge; providing a second cylindrical sector electrode surface defined at a second radial distance from the axis, wherein the second cylindrical sector electrode has an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, and further wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; generating a magnetic field in the ion path; and generating a desired electric field in the ion path perpendicular to the magnetic field using a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces, a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces, and the first and second cylindrical sector electrode surfaces, wherein the first array of electrodes includes at least two circular segment electrodes logarithmically spaced between the upper edges of the first and second cylindrical sector electrode surfaces, wherein the second array of electrodes includes at least two circular segment electrodes logarithmically spaced between the lower edges of the first and second cylindrical sector electrode surfaces, and further wherein generating the desired electric field in the ion path perpendicular to the magnetic field includes applying a predetermined voltage to each of the first and second cylindrical sector electrode surfaces and to each of the logarithmically spaced circular segment electrode of the first and second electrode arrays.
  • 29. The method of claim 28, wherein generating the electric field includes connecting equally valued resistors between adjacent logarithmically spaced electrodes of the first and second arrays of electrodes.
  • 30. A double-focusing mass spectrometry method, the method comprising:providing a first cylindrical sector electrode surfaces defined at a first radial distance from an axis, wherein the first cylindrical sector electrode surface has an upper and lower edge; providing a second cylindrical sector electrode surface defined at a second radial distance from the axis, wherein the second cylindrical sector electrode has an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode, and further wherein an ion path is defined between the first and second cylindrical sector electrode surfaces; generating a magnetic field in the ion path; and generating a desired electric field in the ion path perpendicular to the magnetic field using a first array of electrodes positioned between the upper edges of the first and second cylindrical sector surfaces, a second array of electrodes positioned between the lower edges of the first and second cylindrical sector surfaces, and the first and second cylindrical sector electrode surfaces, wherein generating the desired electric field in the ion path perpendicular to the magnetic field includes configuring the first and second arrays of electrodes as a function of the magnetic field in the ion path such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path such that mass selection using the mass spectrometer is achieved independent of ion velocity.
  • 31. The method of claim 30, wherein configuring the first and second arrays of electrodes includes spacing the first and second array of electrodes as a function of the magnetic field in the ion path such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 32. The method of claim 30, wherein configuring the first and second arrays of electrodes includes shaping the first and second array of electrodes as a function of the magnetic field in the ion path such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 33. A method for use in double focusing mass spectrometer apparatus, the method comprising:providing a non-uniform magnetic field for an ion path of a double focusing mass spectrometer; and forming an electrode assembly to provide an electric field in the ion path, wherein forming the electrode assembly includes forming two or more electrodes to a particular configuration as a function of the non-uniformity of the magnetic field such that the electric field in the entire ion path in the double focusing mass spectrometer is at a predetermined ratio to the magnetic field.
  • 34. The method of claim 33, wherein forming the two or more electrodes includes configuring a first and second array of electrodes positioned generally parallel to one another as a function of the non-uniformity of the magnetic field.
  • 35. The method of claim 34, wherein configuring the first and second arrays of electrodes includes spacing electrodes of the first and second array of electrodes as a function of the non-uniformity of the magnetic field.
  • 36. The method of claim 34, wherein configuring the first and second arrays of electrodes includes shaping electrodes of the first and second array of electrodes as a function of the non-uniformity of the magnetic field.
  • 37. A double focusing mass spectrometry method comprising:sealing two or more substrate portions together to define an ion path, wherein a first substrate portion includes a first array of electrodes formed on a side thereof and wherein a second substrate portion includes a second array of electrodes formed on a side thereof, and further wherein sealing the two or more substrate portions together includes positioning the first and second arrays of electrodes generally parallel to one another; generating an electric field in the ion path using at least the first and second arrays of electrodes, wherein the electric field has a cylindrical geometry; and positioning a first and second magnet pole proximate the two or more substrate portions for providing a magnetic field in the ion path orthogonal to and superimposed with the electric field in the ion path.
  • 38. The method of claim 37, wherein a radial distance along which the first and second array of electrodes are defined is greater than about 10 times a distance in the direction of the axis between the parallel first and second arrays of electrodes.
  • 39. The method of claim 37, wherein the first and second array of electrode includes a first and second array of circular segment electrodes, and further wherein the method includes:providing a first cylindrical sector electrode surface defined at a first radial distance from a cylindrical axis, the first cylindrical sector electrode surface having an upper and lower edge; and providing a second cylindrical sector electrode surface defined at a second radial distance from the cylindrical axis, the second cylindrical sector electrode surface having an upper and lower edge corresponding to the upper and lower edge of the first cylindrical sector electrode surface, the ion path defined between the first and second cylindrical sector electrode surfaces; and further wherein sealing the first and second substrate portions together includes positioning the first array of circular segment electrodes between the upper edges of the first and second cylindrical sector surfaces and positioning the second array of circular segment electrodes between the lower edges of the first and second cylindrical sector surfaces.
  • 40. The method of claim 39, wherein positioning the first array of circular segment electrodes includes evenly spacing the circular segment electrodes between the upper edges of the first and second cylindrical sector electrode surfaces, wherein positioning the second array of circular segment electrodes includes evenly spacing the circular segment electrodes between the lower edges of the first and second cylindrical sector electrode surfaces, and further wherein the method includes applying predetermined voltages to each of the first and second cylindrical sector electrode surfaces and to each of the circular segment electrodes of the first and second electrode arrays.
  • 41. The method of claim 40, wherein applying the predetermined voltages includes forming a first resistor network on a side of the first substrate portion opposite the first array of circular segment electrodes and forming a second resistor network on a side of the second substrate portion opposite the second array of circular segment electrodes.
  • 42. The method of claim 40, wherein applying the predetermined voltages includes applying logarithmically varying voltages across each of the first and second array of electrodes.
  • 43. The method of claim 40, wherein applying the predetermined voltages includes connecting a network of logarithmically varying resistors across each of the first and second arrays of circular segment electrodes.
  • 44. The method of claim 39, wherein the first array of circular segment electrodes includes at least two circular segment electrodes logarithmically spaced between the upper edges of the first and second cylindrical sector electrode surfaces, wherein the second array of electrodes includes at least two circular segment electrodes logarithmically spaced between the lower edges of the first and second cylindrical sector electrode surfaces, and further wherein the method includes applying predetermined voltages to each of the first and second cylindrical sector electrode surfaces and to each of the circular segment electrodes of the first and second electrode arrays.
  • 45. The method of claim 44, wherein applying the predetermined voltages includes forming a first network of resistors having equal values on a side of the first substrate portion opposite the first array of circular segment electrodes and forming a second network of resistors having equal values on a side of the second substrate portion opposite the second array of circular segment electrodes.
  • 46. The method of claim 44, wherein applying the predetermined voltages includes connecting a resistor network of equally valued resistors across each of the first and second arrays of electrodes.
  • 47. The method of claim 37, wherein the method further includes configuring the first and second arrays of electrodes as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 48. The method of claim 47, wherein configuring the first and second arrays of circular segment electrodes includes spacing the first and second arrays of circular segment electrodes as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 49. The method of claim 47, wherein configuring the first and second arrays of circular segment electrodes includes shaping the first and second arrays of circular segment electrodes as a function of the magnetic field such that a desired ratio of magnetic field to electric field is attained in substantially the entire ion path.
  • 50. The method of claim 37, wherein the method further includes depositing the first and second arrays of electrodes on a surface of ceramic substrates.
US Referenced Citations (14)
Number Name Date Kind
3944827 Matsuda Mar 1976 A
3984682 Matsuda Oct 1976 A
4054796 Naito Oct 1977 A
4418280 Matsuda Nov 1983 A
4727249 Bateman et al. Feb 1988 A
4924090 Wollnik et al. May 1990 A
5118939 Ishihara Jun 1992 A
5198666 Bateman Mar 1993 A
5317151 Sinha et al. May 1994 A
5386115 Freidhoff et al. Jan 1995 A
5401963 Sittler Mar 1995 A
5536939 Freidhoff et al. Jul 1996 A
5541408 Sittler Jul 1996 A
5614711 Li et al. Mar 1997 A