U.S. patent number 3,555,273 [Application Number 04/745,836] was granted by the patent office on 1971-01-12 for mass filter apparatus having an electric field the equipotentials of which are three dimensionally hyperbolic.
This patent grant is currently assigned to Varian Associates. Invention is credited to James T. Arnold.
United States Patent |
3,555,273 |
Arnold |
January 12, 1971 |
MASS FILTER APPARATUS HAVING AN ELECTRIC FIELD THE EQUIPOTENTIALS
OF WHICH ARE THREE DIMENSIONALLY HYPERBOLIC
Abstract
A mass filter apparatus for use in mass spectrometers and the
like having an electrode structure capable of generating an
electric field, the equipotentials of which are three dimensionally
hyperbolic and thus avoid the prior art difficulties associated
with discontinuities at the entrance and exit ends of the filter
apparatus.
Inventors: |
Arnold; James T. (Los Gatos,
CA) |
Assignee: |
Varian Associates (Palo Alto,
CA)
|
Family
ID: |
24998451 |
Appl.
No.: |
04/745,836 |
Filed: |
July 18, 1968 |
Current U.S.
Class: |
250/293 |
Current CPC
Class: |
H01J
49/421 (20130101) |
Current International
Class: |
H01J
49/34 (20060101); H01J 49/42 (20060101); H01j
039/34 () |
Field of
Search: |
;250/41.9(2) |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Borchelt; Archie R.
Assistant Examiner: Birch; A. L.
Claims
I claim:
1. A mass filter providing stable transit over its entire operating
length for charged particles having a certain mass-to-charge ratio
comprising:
potential supporting electrode means for creating within a given
volume of space an electric field the instantaneous equipotentials
.phi. of which are described by an equation of the form ##SPC13##
where:
U is a predetermined DC potential; and
V is the peak value of a predetermined AC potential having angular
frequency .omega..
where:
k is a constant;
x, y and z are the orthogonal coordinates of points on a given
equipotential .phi., and r.sub.o is a scaling dimension; and
entrance aperture means disposed at one extremity of said electrode
means for allowing the introduction of charged particles into said
given volume of space;
exit aperture means disposed of another extremity of said electrode
means remote from said entrance aperture means for allowing the
particles for which said field offers a stable transit through said
volume of space to exit from said volume of space; and
means for simultaneously supplying said predetermined AC and DC
potentials to said electrode means for creating said electric
field.
2. A mass filter as defined in claim 1 wherein said electrode means
includes a first electrode the surface of which is in the shape of
an elliptical hyperboloid defined by the equation ##SPC14## and
second and third electrodes having surfaces in the shapes and
dispositions of the elliptical hyperboloid of two sheets defined by
the equation ##SPC15##
3. A mass filter as defined in claim 2 wherein said entrance
aperture passes through said first electrode at ##SPC16## and said
exit aperture passes through said first electrode at ##SPC17##
4. A mass filter as defined in claim 3 wherein said potentials
applied to said electrode means are of the form ##SPC18##
5. A mass filter as defined in claim 1 wherein said electrode means
are comprised of a plurality of elliptical rings disposed relative
to each other in a manner so as to lie on the surfaces of a pair of
imaginary right elliptical cones positioned base to base, the axes
of said cones being coincident with the y axis, and said rings
lying in planes parallel to the x-z plane.
6. A mass filter as defined in claim 5 wherein said rings are
functionally simulated by the truncated boundaries of a plurality
of concentrically disposed elliptical cylinders, said truncated
boundaries being contiguous with the surface of said imaginary
cones.
7. A mass filter as defined in claim 5 wherein said elliptical
rings are uniformly spaced about the y-axis and the potential
applied to said rings is of the form ##SPC19## where:
.phi..sub.n is the potential applied to the n.sup.th ring from the
y-axis;
U.sub.n is the DC potential appointed for the n.sup.th rings;
and
V.sub.n is the peak value of the AC potential having angular
frequency .omega. appointed for the n.sup.th rings.
8. A mass spectrometer for analyzing charged particles
comprising:
a source of charged particles;
a collector means for collecting certain ones of said charged
particles; and
a mass filter separating said source and said collector means and
having an entrance aperture adjacent said source and an exit
aperture adjacent said collector means,
said mass filter further including potential supporting electrode
means for creating within a given volume of space defined by said
electrode means an electric field the instantaneous equipotentials
of which are defined by the equation ##SPC20## where:
U is a predetermined DC potential;
V is the peak value of a predetermined AC potential having an
angular frequency .omega.;
k is a constant;
x, y and z are the orthogonal coordinates of points on a given
equipotential .phi.; and
r.sub.o is a scaling dimension.
9. A mass spectrometer as defined in claim 8 wherein electrode
means are comprised of a plurality of elliptical rings disposed
relative to each other in a manner so as to lie on the surfaces of
a pair of imaginary elliptical cones positioned base to base, the
axis of said cones being coincident with the y-axis, and said rings
lying in planes parallel to the x-z plane.
10. A mass spectrometer as defined in claim 9 wherein said rings
are functionally simulated by the truncated boundaries of a
plurality of concentrically disposed elliptical cylinders, said
boundaries being contiguous with the surface of said imaginary
cones.
11. A mass spectrometer as defined in claim 9 wherein said
elliptical rings are uniformly spaced about the y-axis and the
potential applied to said rings is of the form ##SPC21## where
.phi..sub.n is the potential applied to the n.sup.th ring from the
y-axis;
U.sub.n is the DC potential appointed for the n.sup.th rings;
and
V.sub.n is the peak value of the AC potential having angular
frequency .omega. appointed for the n.sup.th rings.
Description
STATEMENT OF THE INVENTION
This invention relates generally to mass spectrometer apparatus and
more particularly to a novel mass-filtering apparatus for use in a
mass spectrometer.
PRIOR ART
A device designed to transmit charged particles selectively on the
basis of their charge-to-mass ratio by means of electric fields
alone and without requiring the use of any magnetic field was first
described by W. Paul and H. Steinwedel, (Z. Naturforsch 82,448,
(1953). The operating principle of their device was based on the
fact that with certain relationships of DC and AC fields, charged
particles of appropriate charge-to-mass ratio can move stably
through a structure supporting these fields while other charged
particles of different charge-to-mass ratio are unstable and are
rejected from the stable path.
The most familiar prior art devices based on this operating
principle are within the class of devices now known as quadrupole
mass filters. These devices typically consist of a filter section
using four rods of cylindrical or hyperbolic cross section, an
ionizing section at one end of the filter section, and a collector
section at the other end of the filter section. The four rods in
the filter section are symmetrically disposed about a central axis
in such a way that the fields are predominantly transverse to the
central axis and are approximately described by the potential
function .phi. where ##SPC1## where:
.+-. U is the DC potential of the rods;
.+-. V is the peak value of the AC potential of the rods, having
angular frequency .omega.; and
r.sub.o is a scaling dimension.
The dynamics of a charged particle in the fields described by
Equation (1) will conform to the solutions of the equations
##SPC2## where is the charge-to-mass ratio of the charged particle.
The above equations (2) and (3) are forms of the Mathieu
differential equation wherein stable solutions exist only for
certain values of the various coefficients. For example, the
solutions describing the motion in x and y will be stable when
##SPC3## The interval of mass values M.sub.1 .ltoreq.M.sub.S
.ltoreq.M.sub.2, for which the motion will be stable, is greater as
the inequality of the ratio in (5) increases, and the central value
of the stable interval, M.sub.S, is dependent on the value of U or
V.
One difficulty in the prior art lies in the fact that the
structures used define fields which are correct only in the two
dimensional domain. Although there exist fields in the center of
these structures which are suited to the stable transmission of
charged particles of selected charge-to-mass ratio, the fields at
the ends of the structure are in fact disposed so as to reject many
of the desired particles. This situation imposes severe constraints
on the operation of conventional quadrupole mass filters,
particularly when high resolution with high transmission is
desired.
Several proposals have been made to mitigate this difficulty. In a
notable example, Brubaker, (U.S. Pat. No. 3,129,327) has devised
auxiliary electrodes to alter the fields at the entrance to the
filter section. In another, Brubaker (U.S. Pat. No. 3,371,204) has
utilized segmented quadrupole electrodes to improve the entrance
conditions. However, none of the proposals attack the basic problem
of providing fields which lead to stable motions at all points
transversed by the desired charged particle.
OBJECTS OF THIS INVENTION
It is therefore a principal object of this invention to provide a
mass filter means which is not subject to the unstable entrance
conditions which are found in conventional quadrupole mass filters
satisfying the geometric requirements only in a two-dimensional
domain and which includes a structure which when energized produces
electric fields which provide stable transit for certain selected
charged particles at all points traversed between the source and
collector.
Another object of the present invention is to provide a novel mass
filter apparatus which is substantially free of electric field
distortions at the ends of the field-supporting structure where
charged particle injection and extraction take place.
Still another object of the present invention is to provide a mass
spectrometer apparatus including a novel mass filter structure
which provides stable transmission of certain charged particles
over the entire distance between source and collector.
Still other objects and advantages of the present invention will
become apparent after a reading of the following description of
preferred embodiments which are illustrated in the drawing
wherein:
IN THE DRAWING
FIG. 1 illustrates one embodiment of a mass filter in accordance
with the present invention;
FIGS. 1A, 1B and 1C are cross sections of the embodiment shown in
FIG. 1;
FIG. 2 is a stability diagram for the mass filter of the present
invention;
FIG. 3 is an alternative embodiment of the present invention;
FIG. 4 is another alternative embodiment of the present
invention;
FIGS. 4A, 4B and 4C are cross sections of the embodiment shown in
FIG. 4; and
FIG. 5 illustrates an operable mass spectrometer utilizing the mass
filter schematically illustrated in FIG. 4.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
In order to provide stability of transit through the apparatus, the
particles should be launched generally along an axis of the
structure and should begin their transit at an equipotential
surface thereof. By choosing suitable field-creating electrode
geometry allowing access from outside the structure to the
particular equipotential surface selected for ion injection, the
attachment of an ion source with a relatively large aperture will
be permitted.
A generic structure capable of providing stabilizing fields in a
three-dimensional domain is one which provides fields which are
described by the potential ##SPC4## One example of such a structure
is shown in FIG. 1 of the drawing and consists of shaped electrodes
10, 12 and 14 the surfaces of which conform to the family of
elliptical hyperboloids represented by the equations ##SPC5## For
clarity, the intersections of these surfaces with the y-z plane,
the x-y plane, and the x-z plane are shown in FIGS. 1A, 1B and 1C,
respectively.
By the proper application of DC and AC potentials to the electrode
surfaces 10, 12 and 14 described by equations (7) and (8), the
fields described by equation (6) may be achieved within the
structure at all points. It can be shown that a proper selection of
values for U and V will provide the desired stability of transit
along the z-axis for charged particles with charge-to-mass ration
within a desired interval.
In this embodiment an entrance aperture 16 and an exit aperture 17
are provided at the intersections of the z-axis and the electrode
12. The dynamic equations which describe the motion of charged
particles within this particular structure may be written as
##SPC6## No simple analytical expression will establish the values
of U and V and their ratio to give the desired transmission
properties. However, they may be described by noting that in the
limiting case of k .fwdarw. .infin. , the limit of the ratio of U
to V for stability in the x and y directions is the same as (5)
above. Graphical representations of the areas of stable operation
in the x-, y- and z-directions, respectively, may be found by
appropriate scaling of the first stable region of the solutions of
Mathieu's equation as shown in FIG. 2.
In accordance with the conventional treatments, the quantities a
and q of the FIG. may be defined as follows: ##SPC7## On the basis
of these definitions, equations (9)-- (11) have stable solutions in
the regions indicated in the FIG. It will be noted that for any set
of values a and q which fall within the area S, stability of
transit will be provided for charged particles whose charge-to-mass
ratio satisfies equations (12) and (13).
A mass analyzer utilizing this form of the invention includes a
charged particle source 18 disposed at entrance 16, a set of
electrodes 10, 12 and 14 constituting the mass analyzer, and a
charged particle collector 19 disposed at exit 17 all housed in a
suitable vacuum enclosure. The electrodes 10, 12 and 14 which
constitute the mass analyzer are fabricated to conform to the
surfaces shown in FIG. 1 and are described by the equations
##SPC8## Equation (14) describes electrode 12 which is a surface of
a single sheet having a beltlike shape. Equation (15) describes a
surface of two sheets forming the inverted caps 10 and 14 above and
below the beltlike surface 12.
The charged particle source 18 is located on the z-axis at the
aperture 16 in the beltlike electrode 12 at z = - r.sub.0 and is
operated to introduce ions into the mass analyzer. The electrodes
10, 12 and 14 of the mass analyzer are excited by an appropriate
generator of DC and AC potentials to establish an electric
potential distribution within the structure according to equation
(6) such that particles whose charge-to-mass ratio fall within the
selected interval M.sub.1 .ltoreq. M.sub.S .ltoreq. M.sub.2 will
execute stable trajectories through the mass analyzer
structure.
The selected particles may then be collected on a collector
electrode 19 placed outside the mass analyzer structure if the
latter is also provided with an exit aperture 17 at z = + r.sub.0.
In normal operation the collector electrode 19 is connected as
usual to a sensitive electrometer. For greater sensitivity the
simple collector electrode 19 may be replaced by a
converter-electron multiplier detector which is well known in the
art.
Because of the practical difficulties associated with the
fabrication of the hyperboloidal surfaces 10, 12 and 14, it has
been found desirable to consider alternative geometries which are
capable of producing the required field configurations but are less
difficult to fabricate. In FIG. 3 there is shown one such
alternative in which the geometrical requirements of the analyzer
are approximately satisfied. The parallel rods 20, 22, 24 and 26
are disposed in the familiar quadrupole configuration utilized in
the prior art apparatus. However, the electrode rods 22 and 24, the
axes of which lie in the x-z plane, are joined together by a hollow
semicircular section 28 which approximates at the entry region the
shape described by ##SPC9##
A charged particle source 30 is provided in the hollow semicircular
section 28 to allow the injection of charged particles through an
aperture 32 on its inside curved surface. In this example the
structure may be considered as a geometrically similar
approximation to the embodiment described above. The approximation
represented by shaping the electrode section 28 will permit
improvement over the conventional quadrupole structure with the
most important feature of the approximation occurring at the entry
region.
In this example, an exit geometry resembling a conventional
quadrupole mass filter may be employed in spite of the field
distortions since the stability requirements at the exit are
considerably less critical than at the entrance region and may be
otherwise improved by introducing appropriate auxiliary fields, by
means of the ion collector which is used, for the extraction of the
ions. In fact, complete symmetry about the x-y plane in this design
may be less desirable since the approximation used at the entry is
adequate to improve the entry conditions into stable transit
orbits, but is not adequate to provide good focusing of particles
into a small exit. Thus, for this geometry, the subsequent sections
of the mass analyzer and the detection means may be operated
exactly as are quadrupole mass analyzers of conventional
design.
A more desirable embodiment is based on the geometrical
considerations of FIGS. 4, 4A, 4B and 4C. In this embodiment the
desired hyperboloidal potential distribution can be created by an
electrode structure which is comprised of a number of electrical
potential supporting elements in the form of elliptical rings R
which are relatively disposed so as to lie on the boundaries of two
elliptical cones described by the equation ##SPC10##
A set of such elements are shown perspectively in FIG. 4 and the
intersections of these elements with the x-y, y-z and x-z planes
are shown respectively in FIGS. 4A, 4B and 4C.
The elliptical rings R of FIG. 4 are respectively energized so as
to produce within the enclosed area equipotentials of the form
##SPC11## where n is an index number corresponding to a particular
ring R. Moreover, the potentials applied to the respective rings R
are such that the gradient of potential along the rays of the
elliptical cones described by equation (20) is uniform. If the
elements of the electrode structure, i.e., the rings R, are so
disposed that their boundaries mark equal intervals on the conoidal
surface, the desired hyperboloidal potential distribution may be
established within the structure by an excitation which supplies
the elements R with potentials which are uniformly distributed
between ##SPC12## The positioning of the elliptical electrodes R
however, is in no means restricted to an equally spaced
distribution over the imaginary conical surface and may just as
well be spaced in accordance with any suitable distribution scheme.
The illustrated equal spacing is merely for convenience and to
allow the use of a less complex voltage supply means for providing
the field creating potentials to the respective electrodes.
In FIG. 5 there is shown a mass filter structure 31 which is
capable of producing substantially the same equipotential
distribution as that produced by the plurality of elliptical rings
R depicted in FIGS. 4, 4A, 4B and 4C. In this embodiment a set of
elliptical cylinders C of different lengths and radii are
concentrically mounted so that one end of each interior cylinder C
terminates on the surface of an imaginary elliptical conoid. A
second set of similar cylinders C are likewise disposed opposite
the first set so that the opposing terminal edges of the cylinders
C substantially reproduce the ringed structure shown in FIG. 4. The
exterior elliptical cylinder C.sub.7 provides the potential support
surface equivalent to the ring R.sub.7 of FIG. 4 and includes an
entrance aperture 32 and an exit aperture 34 through which the
charged particles are passed.
A source 36 of charged particles which, for instance may be a
source of ions, is disposed proximate the entrance aperture 32 and
is electrically connected to the cylinder C.sub.7 so as not to
cause a perturbing field to be created therebetween. Opposite the
source 36 and adjacent exit aperture 34 there is disposed a
collector electrode 38 which collects the particles passing through
the aperture 34. The source 36, mass filter 31 and collector 38 are
all enclosed in an envelope 39 which is evacuated by a suitable
vacuum pumping means. The collector 38 is operatively connected to
the input of an amplifier 40 which amplifies the collected ion
current before it is fed to a suitable detector means 42 the output
of which is recorded by a recorder 44.
In order to create the desired potential distribution among the
cylindrical electrodes C a plurality of conductors 46 are utilized
to couple the various cylinders C to a voltage divider 48 which is
energized by an AC- DC power source 50. A plurality of capacitors
52 are provided for coupling the AC energy to the electrodes C in a
manner to produce the desired distribution of AC potentials in the
same proportionate distribution as is the case with the differing
DC potentials applied thereto.
In operation, mass filters in accordance with the present invention
provide for motion which is, for particles of the desired
charge-to-mass ratio, bounded in the x and y directions. The motion
is unbounded in the z-direction primarily for the reason that the
injection energy of the particles is greater than the energy of
motion in the z-direction which may be bounded between the
injection and detection apertures. There is, in fact, no strict
requirement that the operating point be chosen such that the motion
in the z-direction be bounded in any limits; the operating point
being determined by the ratio of DC to AC potentials applied to the
electrodes and the sense of the DC potentials.
After having read the above disclosure, many more alterations and
modifications of the invention will be apparent to those of skill
in the art and it is to be understood that this description of
preferred embodiments is for purposes of illustration and is in no
manner intended to be limiting in any way. Accordingly, I intend
that the appended claims be interpreted as covering all
modifications which fall within the true spirit and scope of my
invention
* * * * *