U.S. patent number 3,852,595 [Application Number 05/290,900] was granted by the patent office on 1974-12-03 for multipoint field ionization source.
This patent grant is currently assigned to Stanford Research Institute. Invention is credited to William H. Aberth.
United States Patent |
3,852,595 |
Aberth |
December 3, 1974 |
MULTIPOINT FIELD IONIZATION SOURCE
Abstract
A field ionizing source for ionizing components of a gas sample
includes a multipoint array of conductive needle-like elements on a
porous substrate. A grid is disposed in close proximity to the
needle-like elements so that an ionizing electric field is
generated between individual needle-like elements and the grid when
a potential difference is established between the grid and array.
The gas sample is introduced into the ionizing electric field zone
by passing it through the back of the porous substrate and into the
array between the needle-like elements so that substantially all of
the gas is exposed to the ionizing electric field. Ions so produced
are formed into an ion beam by a focusing electrode structure and
directed into a spectrum analyzer and components of the gas sample
are determined.
Inventors: |
Aberth; William H. (Palo Alto,
CA) |
Assignee: |
Stanford Research Institute
(Menlo Park, CA)
|
Family
ID: |
23117976 |
Appl.
No.: |
05/290,900 |
Filed: |
September 21, 1972 |
Current U.S.
Class: |
250/288;
250/423F; 313/309; 250/292; 250/423R; 313/351 |
Current CPC
Class: |
H01J
49/168 (20130101); H01J 27/26 (20130101); H01J
2237/0807 (20130101) |
Current International
Class: |
H01J
27/26 (20060101); H01J 49/16 (20060101); H01J
27/02 (20060101); H01J 49/10 (20060101); H01j
039/36 (); H01j 001/30 () |
Field of
Search: |
;313/309,351
;250/41.9G,41.9SE,41.9SR,282,285,288,423 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
Primary Examiner: Lawrence; James W.
Assistant Examiner: Punter; Wm. H.
Attorney, Agent or Firm: Faubion; Urban H.
Claims
What is claimed is:
1. A field ionization source comprising a plate-like porous
substrate pervious to flow of substantially all gases and a
multiplicity of needle-like elements located on one surface of said
substrate, said needle-like elements being highly uniform in space
and uniformly spaced on said substrate.
2. A field ionization source, as defined in claim 1, wherein both
said substrate surface on which the needle-like elements are
deposited and said needle-like elements consist of conductive
material.
3. A field ionization source comprising a plate-like porous
substrate pervious to flow of substantially all gases and a
multiplicity of needle-like elements located on one surface of said
substrate, said substrate having uniformly spaced land areas
thereon defined by uniformly spaced apertures therethrough which
provide the porosity, said needle-like elements being highly
uniform in space, uniformly spaced on said substrate, comprised of
conductive material and located on the said land areas of said
substrate.
4. A field ionization source, as defined in claim 3, wherein said
plate-like substrate is of a substantially nonconductive material
with a plate-like conductive electrode at least on one surface
thereof, said plate-like electrode having aperture therein in
registry with the apertures in said nonconductive substrate and
said conductive needles located on said conductive electrode.
5. A field ionization source for ionizing components of sample
gases, including the structure defined in claim 1, and means to
introduce a sample gas to be analyzed to the surface of said
plate-like substrate opposite that occupied by said needle-like
elements whereby sample gas flow is provided through said porous
substrate and around said needle-like elements, grid means spaced
from said needle-like elements and means for applying a potential
between said grid and said needle-like elements thereby to provide
an electric field therebetween whereby the said gas sample is
exposed to the said electric field in the area of said needle-like
elements and molecules of said gas sample are thereby ionized.
6. A field ionization source for ionizing components of sample
gases, including the structure defined in claim 2, and means to
introduce a sample gas to be analyzed to the surface of said
plate-like substrate opposite that occupied by said needle-like
elements whereby sample gas flow is provided through said porous
substrate and around said needle-like elements, grid means spaced
from said needle-like elements and means for applying a potential
between said grid and said needle-like elements thereby to provide
an electric field therebetween whereby substantially all of the
said gas sample is exposed to the said electric field in the area
of said needle-like elements.
7. A field ionization source for ionizing components of sample
gases, including the structure defined in claim 3, and means to
introduce a sample gas to be analyzed to the surface of said
plate-like substrate opposite that occupied by said needle-like
elements whereby sample gas flow is provided through said porous
substrate and around said needle-like elements, grid means spaced
from said needle-like elements and means for applying a potential
between said grid and said needle-like elements thereby to provide
an electric field therebetween whereby the said gas sample is
substantially all exposed to the said electric field in the area of
said needle-like elements.
8. A field ionization source for ionizing components of sample
gases, including the structure defined in claim 4, and means to
introduce a sample gas to be analyzed to the surface of said
plate-like substrate opposite that occupied by said needle-like
elements whereby sample gas flow is provided through said porous
substrate and around said needle-like elements, grid means spaced
from said needle-like elements and means for applying a potential
between said grid and said needle-like elements thereby to provide
an electric field therebetween whereby the said gas sample is
substantially all exposed to the said electric field in the area of
said needle-like elements.
9. A mass spectrometer, including the structure as defined in claim
5, including means to focus said ions into an ion beam and means to
analyze ions in said beams whereby constituent components of said
sample gas are determined.
10. A mass spectrometer, including the structure as defined in
claim 6, including means to focus said ions into an ion beam and
means to analyze ions in said beams whereby constituent components
of said sample gas are determined.
11. A mass spectrometer, including the structure as defined in
claim 7, including means to focus said ions into an ion beam and
means to analyze ions in said beams whereby constituent components
of said sample gas are determined.
12. A mass spectrometer, including the structure as defined in
claim 8, including means to focus said ions into an ion beam and
means to analyze ions in said beams whereby constituent components
of said sample gas are determined.
Description
BACKGROUND OF THE INVENTION
The phenomenon of ionization plays a significant role in many
scientific instruments and experiments, e.g., in ionization gauges
and mass spectrometers. In mass spectrometry, an unknown material
under investigation is ionized prior to injection into the analyzer
or mass-separator section of the mass spectrometer. Ionization is
usually produced by electron impact with the unknown material,
utilizing a suitable electron source such as a thermionic emitter.
However, electron impact with molecules not only ionizes them, but
also tends to fragment them into two or more species, so that the
mass spectrum, obtained by this ionization method, may show the
presence of the daughter species but little or nothing of the
parent species. Moreover, if any of the daughter species is the
same as, or has a mass-to-charge ratio approximately equal to,
another species originally present in the unknown material, then
the mass spectrum obtained can be difficult or impossible to
interpret correctly regarding the original constitutents of the
unknown material.
In some applications where mass spectrometry is used to monitor or
control other processes, e.g., the preparation of photoemissive
surfaces, the use of a thermionic emitter for ionization is
disadvantageous because the heat or light from the emitter tends to
disturb the process. The use of a cold nonluminous ionizer in such
applications constitutes a significant improvement. Field
ionization, a phenomenon in which molecules entering a region of
very high electric field (10.sup.8 to 10.sup.9 V/cm) are ionized by
extraction of electrons by the field, causes substantially less
fragmentation than electron-impact ionization. Also, this
phenomenon does not require or involve the generation of light or
heat.
In order to reduce to a practical level the voltage required for
producing the required high fields, sharp blades, needles or points
are used as field ionizing electrodes, a counterelectrode is spaced
from the needle-like structures and a voltage is applied so that
the counterelectrode is negative relative to the blades or
needle-like structures. However, even with the use of sharp points,
if the counterelectrode is spaced a macroscopic distance from the
blades or points, e.g., of the order of millimeters, the voltages
required for the field ionization are of the order of tens of
kilovolts.
Ionization efficiency of prior art field ionizers of the single
blade or single needle-like structure is low since the effective
region where ionization takes place is confined to the small volume
in the pg,3 immediate vicinity of the apex of the sharp point or
blade edge, so that the rate of ion production for a given pressure
of material to be analyzed is much lower for field ionization than
for electron-impact ionization. Another reason is that the
field-produced ions attain velocities equivalent to the voltage
applied between ionizer and counterelectrode and the ions are
impelled away from the ionizer over a wide range of angles, so that
only a small fraction of the ions is collimated into a beam
suitable for injection into the analyzer of the mass spectrometer
without employing complex ion-optical lenses.
Parallel operation of many needle-like members to provide a
correspondingly large ionization volume is feasible, but the
problems of formation of the parallel structures and providing
ion-optical collimation are formidable. For example, ion-optical
collimation is practical only if emission energies of the ions can
be kept small, which necessitates spacings between the ionizer and
counterelectrode of the order of microns with the ionizer point
having a tip radius of a fraction of a micron, e.g., 0.1 micron.
Also, it is desirable to space the needle-like structures as close
together as possible without incurring significant decrease of the
field at each point by the presence of its neighbors.
Many of the problems involved in the construction of arrays of the
fine needle-like structures and the problems thought to be inherent
in parallel operation of such structures have been solved by
structures and methods of producing the structures as disclosed in
U.S. Pat. No. 3,453,478, entitled "Needle-Type Electron Source,"
issued July 1, 1969, and U.S. Pat. No. 3,497,929, entitled "Method
of Making a Needle-Type Electron Source," issued Mar. 3, 1970, to
Kenneth R. Shoulders and Louis N. Heynick. Further refinements are
illustrated and described in U.S. Pat. No. 3,665,241, entitled
"Field Ionizer and Field Emission Cathode Structures and Methods of
Production," issued May 23, 1972, to Charles A. Spindt and Louis N.
Heynick. The subject matter of these patents is specifically
incorporated by reference.
A highly refined and practical field ionization source is provided
using the teachings of the above patents. A bare-point structure is
provided in which a regular array of closely spaced metallic points
of controlled geometry is provided over the surface of a conductive
substrate and a screen-like counterelectrode is placed in close
proximity to the points of the needle-like elements with apertures
in the screen-like counterelectrode in register with the points. A
field ionization structure is provided by making the
counterelectrode of the arrangement just described negative
relative to the substrate electrode and providing the proper
electrode counterelectrode spacing as well as ratio of such space
to the distance between electrode points. The sample to be ionized
is introduced in the area of the needle-like structures.
While the field ionization just described is highly efficient
relative to prior art field ionization sources, it is still
desirable to increase the ratio of sample particles ionized to
sample particles introduced, i.e., increase the efficiency of
ionization. This is especially critical in the many applications
where the total sample of the material to be analyzed is very
small.
SUMMARY OF THE INVENTION
In carrying out the present invention, a field ionization source
for ionizing components of a gas sample is provided by utilizing a
highly regular array of closely spaced needle-like points of
controlled geometry on the surface of a porous substrate. An
electric field is provided in the area of needle-like elements by
disposing a conducting grid in close proximity of the needle-like
elements with apertures in the grid in register with the points of
the needle-like elements and providing a potential difference
between the grid and needle-like elements. The gas sample to be
ionized is introduced into the ionizing electric field zone by
passing it through the porous substrate and into the ionizing
electric field around the needle-like elements so that
substantially all of the gas passes in close proximity to the
ionizing electric field, thus increasing the probability of
ionization.
The novel features which are believed to be characteristic of the
invention are set forth with particularity in the appended claims.
The invention itself, however, both as to its organization and
method of operation, together with further objectives and
advantages thereof, may best be understood by reference to the
following description taken in connection with the accompanying
drawings.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an enlarged perspective view showing a bare-point array
utilized in the field ionization source of one embodiment of the
invention;
FIG. 2 is an enlarged fragmentary prospective view of a bare-point
array using a different substrate arrangement (different from the
one illustrated in FIG. 1) for one embodiment of the field
ionization source;
FIG. 3 is a central, vertical, sectional view of a field ionization
source structure utilizing the bare-point array of FIG. 1; and
FIG. 4 is a diagrammatic cross-sectional view of a mass
spectrometer utilizing the field ionization source.
DESCRIPTION OF PREFERRED EMBODIMENTS
A form of the basic bare-point array 10 used as a field ionization
source is illustrated in FIG. 1. The bare-point array structure 10
includes a supporting disk-like substrate 11 and an array of
electric field-forming needle-like bare points 12 formed thereon.
Since an important consideration in the design of the source is to
provide a way to bring the sample to be ionized directly into the
ionizing electric field for most efficient ionization, the
substrate is made porous so that the sample can be brought in
through the back of the substrate and up along the surface of the
field-forming needle-like elements 12. As illustrated, the bare
points are pyramidal but may be of other conical shapes. The
substrate 11 in this embodiment is of porous sintered tungsten
which is conductive and, therefore, along with the array of
needle-like points 12 formed thereon, constitutes a conductive
electrode. In one embodiment, the tungsten substrate 11 is 65
percent porous and the needle-like points 12 cover a circular area
1.5 millimeters in diameter and are spaced 0.0025 centimeter apart
(center-to-center).
For some applications the permeability of the porous tungsten
substrate 11 may not be sufficient or it may not have the
characteristics desired. For example, though tungsten is considered
inert, it may, in fact, chemically affect particular samples;
therefore, it may be preferable to use a semiconductive or an
insulative substrate. One such embodiment is illustrated in FIG. 2.
The substrate 14 illustrated in FIG. 2 constitutes a glass disk 16
which has a myriad of open channels 18 all of the way through the
disk. A practical disk substrate 16 for the array is about 1.5
millimeters in diameter with about 60 percent of the disk
comprising straight, open channels.
Thus, it is seen that the substrate is highly porous and shows
little resistance to gas flow-through. In order to provide a
conductive electrode, the upper surface of the substrate 14 is
provided with a layer of conductive or semiconductive material 20
which does not cover (does not close) the open channels 18 in the
substrate 14 and the array of needle-like elements 22 which are
used to form the ionizing electric field are laid down on the
conductive coat 20 on lands defined by the substrate surface area
between the open channels 18. The array of needle-like elements 22
and 12 in the embodiments of both FIGS. 1 and 2 may be resistive,
semiconductive, insulative or composite materials and their
surfaces overcoated or otherwise treated to obtain the desired
characteristics just as taught in the patents previously referred
to. Further, the arrays of needle-like elements may be formed as
described in those patents.
The disk-shaped glass substrates are available commercially from
Bendix Corporation and Varian Associates and are used for other
purposes. The plate consists of microscopic hollow glass channels
fused into a disk-shaped array. The disk is practically obtainable
in sizes ranging up to 25 millimeters in diameter (a diameter about
equivalent to that of a quarter), about 5 millimeters thick (about
one third the thickness of a quarter), and contains approximately
1,670,000 open channels. Thus, about 60 percent of the disk is
comprised of open channels. Such disks are shown and described in
the catalog entitled "Application for Microchannel Plates,"
published by Varian, Palo Alto Tube Division. The surface of the
microchannel plates, including the interior of the channels as
described in the catalog, is semiconductive and the plates
described are entirely suitable as substrates for the field-forming
arrays for the present field ionization source. Other practical
insulative substrates are made of sintered glass and porous
alumina.
A setting for the bare-point array 10 of FIG. 1 is illustrated in
FIG. 3. The field ionization source 30 illustrated in FIG. 3 is
designed specifically to provide a convenient way to direct the
flow of a gas sample through the back of the porous sintered
tungsten substrate 11 and up around the electrical field-forming
needle-like elements 12. The field ionization source 30,
illustrated, also provides means for providing electrical
connections to elements of the source in order to generate the
ionizing field. The gas flow channel 32 to the back of the sintered
plug 11 is identified by a series of arrows which extend directly
through the device. Electrical connections must be made to the
sintered tungsten plug 11 and a field-forming grid structure 34
spaced from and parallel to the plane of the ionizing points on the
needle-like field ionizer 12.
Consider first the physical mounting structure for the multipoint
ionizing array 10 which also serves as the conductive electrical
connection thereto. The source 30 is constructed so that it is
easily removable in order to be able to replace a damaged or
inactive multipoint array 10. The sintered tungsten plug 11 of the
array 10 is mounted at one end (right in the figure) of a tubular
conductive array support member 36 as by brazing or welding. In
order to provide a means for removably mounting the support tube 36
to a supporting conductive washer or collar 38, the tubular member
36 is threaded internally at its opposite (left) end (at 37) so as
to receive the external threads of a bolt 40 which extends up
through a centrally located threaded aperture 39 in the support
collar 38 and also threads into the internal threads 37 of the
support tube 36. The collar 38 is also provided with a recess 41 to
receive the head of the securing bolt 40. In order to provide a
clear open channel for gas flow to the back of the sintered
tungsten plug 11, a bore or channel 42 is provided through the
securing bolt 40. The structure thus far described is rigidly held
together as a unit, is electrically conductive so that the
electrical connections can be made to the multipoint field ionizer
array 10, and has a clear opening to the back of the multipoint
array so that a gas sample may be introduced.
In order to secure the multipoint field ionizer assembly, just
described, to the instrument in which it is to be used, here a mass
spectrometer, the instrument itself is provided with a highly
conductive heat sink and ion source support 46 which is illustrated
as a heavy cylindrical copper bar 46 provided with a centrally
located longitudinal aperture, that forms part of the gas flow
channel 32, and external threads around the upper end. The field
ionizer assembly is then secured to the rod-like heat sink 46 by an
internally threaded conductive cap 48 that threads on to the outer
end (threads 47) of the heat sink 46 and has an inwardly extending
annular lip 49 that fits snugly into an annular recess 50 around
the outer periphery of the collar 38 of the field ionizer assembly.
In order to provide a good electrical and thermal conduction
between the heat sink 46 and the field ionizer assembly mounted
thereon, washer 52 of relatively soft, highly conductive material
is provided between the upper surface of the heat sink 46 and the
lower surface of the field ionization source supporting washer 38.
Gold is a highly acceptable material for washer 52.
Thus, it is seen that a clear gas flow channel 32 is provided
through the heat sink 46, the supporting bolt 40 and tubular
multipoint field ionizer array support member 36 to the back of the
porous sintered tungsten plug 11. Further, all of the parts thus
described are conductive of both heat and electrical current. Thus
a common path conductive of both heat and electricity is provided
for the multipoint field ionizing array 10. Since a potential
difference must be established between the grid 34 of the
ionization source and the needle-like points 12 of the array 10, a
tubular insulating grid support member 54 is mounted on the upper
surface of the field ionization assembly support collar 38 so that
it surrounds the support tube 36 of the multipoint array 10 and is
concentrically spaced therefrom. The length of the insulating
tubing member 54 is such that the grid 34 is spaced above the plane
of the ionizing points of the needle-like elements 12 by the
appropriate distance.
In the source illustrated here, the grid 34 is a mesh of 400 lines
per centimeter, is spaced about 0.0125 centimeter above the points
with the openings therein positioned in register with the points of
the needle-like elements 12. The grid 34 is firmly secured in place
on the upper end of the insulating tube 54 by a plug-like stainless
steel cap 56 which is open in the center to allow egress of ions
formed by the source. Retaining cap 56 is provided with appropriate
threaded screw recesses 58 extending through its upper surface and
screw recess 59 which extends through its outer periphery. Set
screws 60 are provided in the screw recesses to 58 and 59 to engage
the upper end and outer periphery, respectively, of the supporting
insulating tube 54 to hold the cap 56 firmly in position.
The insulating tube 54 is firmly secured to the upper surface of
the support collar 38 of the field ionization source by a clamp
arrangement. Specifically, an annular retaining groove or recess 51
is provided around the periphery of the grid support member 54 near
the end opposite the grid 34. A hold down collar or washer 53 is
positioned in the retaining groove 51. The grid assembly hold down
arrangement is completed by hold down bolts 55 that pass through
apertures in the hold down collar 53 and are threaded into
internally threaded apertures 35 provided in the upper surface
(toward the grid 34) of the source supporting washer 38. Thus, the
grid 34 is properly positioned relative to the multipoint elements
12 and held firmly in place.
The field ionization source 30 is shown, diagrammatically, in a
mass spectrometer (the setting where it is used) in FIG. 4. Since
the mass spectrometer, aside from the novel ion source and the
novel combination, is conventional, it is illustrated only
diagrammatically and not in great detail. A vacuum-tight envelope
60 is provided to enclose the entire mass spectrometer. The
multipoint field ion source is illustrated in one end immediately
followed by conventional focusing electrodes 62 which collimate the
ions developed by the multipoint ion source 30 into a stream and
direct the stream into a conventional quadrupole analyzer section
64. A conventional ion collector 77 is provided at the opposite end
of the mass spectrometer to receive transmitted ions. As is usual,
a vacuum pump 68 is connected to maintain the proper vacuum in the
spectrometer envelope 60.
For operation in the intended manner, the gas flow channel 32 from
the back of the porous tungsten plug 11 of the multipoint field
ionizer array 10 may be traced back through a supply line 70 to a
source of sample gas 72. The gas flow entry channel 32 is provided
with an on-off valve 74 so that the channel may be closed entirely
and also a variable leak valve 76 for fine control of the sample
admitted for ionization. For normal field ionization operation, a
point to grid potential difference of 3,645 volts is applied. The
quadrupole section used has pole pieces 1.6 centimeters in diameter
and 22 centimeters long. The multipoint source 30 is maintained at
+45 volts and the extraction grid 34 kept at -3,600 volts. The ions
leaving the grid are decelerated and focused by a single aperture
electron optical lens 62 with a potential of about -400 volts. The
field produced ions enter quadrupole ionizer section 64 through a 5
millimeter aperture with a net energy of 45 ev. Using toluene as
sample gas, an ionization efficiency of about 1 in 3,000 and a
transmision efficiency of 1 in 330 is obtained. Thus, for every
million sample molecules of toluene, one is ionized, massed
analyzed, and detected.
In order to obtain a comparison of results between ionization using
the multipoint field ion source 30, as just described, and using
the same source bringing the sample into the area of the multiple
points from the side or top rather than through the porous sintered
tungsten plug 11, a second supply line 80 is connected to the
sample source 72 just prior to an on-off valve 82 in the regular
gas flow channel 32. The second supply line 80 is connected to
provide entry of sample gas into the mass spectrometer envelope 60
along the side in the region of the multipoint array 10. The
auxiliary supply line 80 is also provided with an on-off valve 84
to allow the line to be opened and closed. By closing on-off valve
82 in the normal supply line 70 and opening the normally closed
valve 84 in auxiliary supply line 80, the sample effluent from
variable leak valve 74 is diverted directly into the spectrometer
envelope 60. The signal obtained with the same sample flow using
the channel through the sintered tungsten array support and the
sample flow to the side of the array is 550 times as strong, thus
showing the improvement provided by the present invention over the
next best known field ionization source.
While particular embodiments of the invention are shown, it will be
understood that the invention is not limited to the specific
structures since many modifications may be made both in the
material and the arrangement of elements. It is contemplated that
the appended claims will cover such modifications which fall within
the true spirit and scope of the invention.
* * * * *