U.S. patent number 3,770,954 [Application Number 05/213,525] was granted by the patent office on 1973-11-06 for method and apparatus for analysis of impurities in air and other gases.
This patent grant is currently assigned to General Electric Company. Invention is credited to William D. Davis.
United States Patent |
3,770,954 |
Davis |
November 6, 1973 |
METHOD AND APPARATUS FOR ANALYSIS OF IMPURITIES IN AIR AND OTHER
GASES
Abstract
Mass spectrometric analysis of trace impurities including
particulate matter in air or other gas utilizes a heated metallic
filament on which a sample of the gas is impinged to generate short
bursts of ions of the impurity (in the case of particulates) by
surface ionization. The gas sample is introduced to the heated
filament by passage through a thin tube and impingement on a very
small hole prior to entering the chamber in which the filament is
located. A pump removes most of the gas between the tube and hole
and the particles passing through the hole are directed at the
heated filament. An ion lens generates an electric field which
withdraws the ions from the heated filament surface and a
conventional mass analyzer is used for mass analysis of the
ions.
Inventors: |
Davis; William D. (Albany,
NY) |
Assignee: |
General Electric Company
(Schenectady, NY)
|
Family
ID: |
22795444 |
Appl.
No.: |
05/213,525 |
Filed: |
December 29, 1971 |
Current U.S.
Class: |
250/288; 250/299;
250/425; 250/424; 250/431 |
Current CPC
Class: |
H01J
49/16 (20130101) |
Current International
Class: |
H01J
49/16 (20060101); H01J 49/10 (20060101); H01j
039/34 (); B01d 059/44 () |
Field of
Search: |
;250/41.9SE,41.9SB,41.9S
;313/63 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Borchelt; Archie R.
Assistant Examiner: Church; C. E.
Claims
What I claim as new and desire to secure by Letters Patent of the
United States is:
1. A mass spectrometer for the analysis of impurity particles
including particulates in a gaseous medium utilizing surface
ionization to produce the ions to be analyzed and comprising
a first chamber,
first pump means for developing and maintaining a vacuum in the
order of 10.sup..sup.-5 torr within said first chamber,
a metal filament of a metal having a high work function especially
when oxygen covered and positioned within said first chamber,
a second chamber located in said first chamber and partitioned
therefrom, said second chamber maintained at a vacuum having a
pressure of magnitude several orders higher than the vacuum in said
first chamber,
a tube having a first end external of said first and second chamber
and open to a gas sample being analyzed for particular impurity
particles including particulates, and a second end located in said
second chamber, the second end of said tube aligned with a small
hole in a wall partitioning the second chamber from the first
chamber to thereby substantially reduce passage of the gaseous
medium into the first chamber while permitting passage of the
impurity particles thereto, the second end of said tube also
aligned with a major surface of said filament for directing the
impurity particles toward said filament for impingement thereon,
the gas sample passing continuously through said tube for obtaining
continuous analysis of the particular impurity particles including
particulates.
means for heating said filament to a temperature in a range between
700.degree. and 1,700.degree. C., the particular operating
temperature of said filament being determined by the particular
impurity particle to be analyzed,
means positioned within said first chamber adjacent the heated
filament for establishing an electric field for withdrawing from a
surface of said filament ions of the impurity particles in the gas
sample generated as short bursts of ions by surface ionization, and
for focussing the ions into a thin line beam thereof,
means positioned within said first chamber adjacent the electric
field means and remote from said filament for defining the width of
the thin line ion beam,
mass analyzer means in communication with said ion beam width
defining means for separating the ions according to their mass and
selecting the ions of the particular impurity desired to be
analyzed, and
ion detector means in communication with said mass analyzer means
for sensing the selected ions desired to be analyzed, the number of
ions per burst sensed by said ion detector means being a measure of
the amount of the particular impurity per particulate, a single ion
representing a single molecule of the impurity.
2. The mass spectrometer set forth in claim 1 wherein
said second chamber is maintained at a vacuum in the order of 1
torr.
3. The mass spectrometer set forth in claim 1 and further
comprising
second pump means connected to said second chamber for developing
and maintaining a vacuum in the order of 1 torr therein.
4. The mass spectrometer set forth in claim 1 and further
comprising
a valve in said tube for controlling the flow of the gas sample
into said first chamber whereby the aseous medium is sampled over
selected time intervals.
5. The mass spectrometer set forth in claim 1 and further
comprising
means for reducing background of ions occuring in said first
chamber from sources other than the gas sample,
6. The mass spectrometer set forth in claim 1 wherein
the small hole is of diameter approximately 0.002 inch.
7. The mass spectrometer set forth in claim 1 wherein
said metal filament is a u-shaped ribbon.
8. The mass spectrometer set forth in claim 7 wherein
said metal ribbon filament is fabricated from a metal selected from
the group consisting of rhenium, tungsten, iridium and
platinum.
9. The mass spectrometer set forth in claim 7 and further
comprising
means for rigidly supporting said metal ribbon filament, said
electric field means and said ion beam width defining means in
fixed alignment.
10. The mass spectrometer set forth in claim 9 wherein
said supporting means comprise
a plurality of electrically nonconductive posts having first ends
rigidly connected to a first side of said first chamber,
an electrically nonconductive member rigidly connected to second
ends of said posts,
said electric field means and said ion beam width defining means
rigidly connected along the length of said posts, and
a pair of electrically conductive plate members rigidly connected
to said electrically nonconductive member in spaced apart coplanar
relationship, ends of said u-shaped metal ribbon filament rigidly
connected to said electrically conductive plate members,
said filament heating means consisting of a pair of electrical
conductors connected to said electrically conductive plate members
and to a source of electric power.
11. The mass spectrometer set forth in claim 10 wherein
said electrically nonconductive member is provided with an aperture
therethrough oriented in alignment with the spacing between said
pair of electrically conductive plate members, and
a viewing port located in a second side of said first chamber
opposite the first side for permitting viewing of said metal ribbon
filament through the aperture in said electrically nonconductive
member during operation of the spectrometer.
12. A method for the analysis of impurity particles including
particulates in a gaseous medium comprising the steps of
introducing a gas sample being analyzed for particular impurity
particles into a irst end of a tube located external of both a
first chamber and second chamber located in the first chamber but
partitioned therefrom,
exiting the gas sample from the second end of the tub located in
the second chamber,
developing and maintaining the second chamber at a rough vacuum
having a pressure of magnitude several orders higher than the
vacuum in the first chamber,
directing the gas sample exiting from the second end of the tube at
a small hole in a wall partitioning the second chamber from the
first chamber to thereby substantially reduce passage of the
gaseous medium into the first chamber while permitting pasage of
the impurity particles thereto,
directing the impurity particles upon passage through the small
hole toward a filament positioned in the irst chamber for
impingement thereon,
developing and maintaining a vacuum in the order of 10.sup..sup.-5
torr within said first chamber,
heating the filament to a temperature in a range between
700.degree. and 1,700.degree. C., the particular operating
temperature of the filament being determined by the particular
impurity particle to be analyzed and causing surface ionization of
the impurity particles impinging on the filament,
establishing an electric field in the vicinity of the filament for
withdrawing ions of the impurity particles in the gas sample from
the surface of the filament and for focussing the ions into a thin
line beam thereof, the ions being generated as short bursts of
ions, the number of ions per burst being determined by the amount
of the particular impurity per particulate and a single ion
representing a single molecule of the impurity,
passing the thin line ion beam through at least one slitted plate
member for defining the width of the thin line ion beam,
passing the defined ion beam into a mass analyzer for separating
out the particular ions desired to be analyzed from other ions
which may also occur in the first chamber, and
detecting the particular ions desired to be analyzed to thereby
determine the amount of the impurity particles in the gaseous
medium.
13. The method set forth in claim 12 wherein
the step of exiting the gas sample from the second end of the tube
consists of continuously passing the gas sample through the tube
for obtaining continuous analysis of the gas medium.
14. The method set forth in claim 13 wherein the steps of impinging
the gas sample on the filament, heating the filament and developing
the vacuum may all be done simultaneously.
15. The method set forth in claim 12 and further comprising the
step of
controlling the flow of the gas sample into the first chamber for
obtaining analysis of the gaseous medium over selected time
intervals.
16. The method set forth in claim 15 wherein the steps of impinging
the gas samle on the filament, heating the filament, and developing
the vacuum consist of
impinging the gas sample on the filament for a predetermined
interval in the absence of the 10.sup..sup.-5 torr vacuum in the
first chamber, then developing the 10.sup..sup.-5 torr vacuum at
the termination of the air sample interval, and finally heating the
filament upon developing the 10.sup..sup.-5 torr vacuum.
17. The method set forth in claim 12 and further comprising the
step of
developing and maintaining the rough vacuum in the order of 1 torr
in the second chamber.
Description
My invention relates to mass spectrometric analysis of impurities
in a gas, and in particular, to a method and apparatus utilizing
surface ionization of the impurities on a heated filament for
producing the impurity ion which is analyzed by a conventional mass
analyzer.
Mass spectrometers have long been used for the analysis of trace
gaseous impurities in air and other gases, and the simple mass
spectrometer usually utilizes a conventional electron bombardment
ion source for generating the ions of contaminant molecules to be
analyzed. A mass spectrometer using only a single stage of mass
separation is limited in its application by reduced sensitivity due
to the generally broad background of scattered ions, principally
N.sub.2 and O.sub.2 that are ionized as normal gases in an air
sample and arrive at the detector of the mass spectrometer either
by gas scattering or bouncing off the walls of the analyzer tube.
The magnitude of this background depends on mass position and gas
pressure which typically makes analysis below one part per million
(p.p.m.) difficult. More complicated mass spectrometers using
additional stages of mass analysis and, or energy analysis, to more
effectively filter out these unwanted gas ions can reduce the
background to the p.p.b. range or lower, but at this level,
discrete ion peaks due to a multitude of various kinds of
ion-molecule reactions and other side effects becomes a major
problem and the instrument is no longer small and simple. The
ion-molecule reactions occur, for example, by reactions between the
various ions of N.sub.2, O.sub.2, Ar, H.sub.2 O and other common
air constituents. Electrons hitting the surfaces of the ion source
can also produce unwanted ions. To eliminate these problems, it
would be desirable to ionize only the impurities in the air or
other gas and not the more common major components in such air or
other gas sample.
Continuous analysis of particulate matter in the gas sample
presents additional problems for the conventional mass spectrometer
since the introduction of the sample cannot be accomplished with a
simple gas leak. The only previously known method has been to
collect the sample on a filter and then by mechanical means or by
chemical treatment, transfer the sample from the filter to the ion
source of the spectrometer. Electron bombardment ion sources can
only be used if the sample is vaporized separately and this would
probably decrease the net yield of ions. Finally, the particles
which can be analyzed by means of electron bombardment ion sources
are generally limited to molecules and do not include particulate
matter.
Therefore, one of the principal objects of my invention is to
provide direct mass spectrometric analysis of trace impurities in a
gas by utilizing surface ionization to produce the ions to be
analyzed.
Another object of my invention is to provide mass spectrometric
analysis of particulate matter in a gas sample by utilizing the
surface ionization process.
Another object of my invention is to obtain the mass spectrometric
analysis on a continuous basis.
A further object of my invention is to obtain the mass
spectrometric analysis by ionizing only the contaminant particles
and not the major components of the gas sample.
A still further object of my invention is to provide a method and
apparatus for the mass spectrometric analysis of trace impurities
in a gas sample which has a higher sensitivity than conventional
simple mass spectrometers and is of simple construction.
Briefly stated, my invention is a method and apparatus for the
analysis of impurities in air and other gases which utilizes
surface ionization to produce the ions of the contaminant particles
without ionizing the major components in the gas sample. Particles
are defined herein as including both molecules and particulate
matter. The gas sample is introduced to a heated filament by
passage through a thin tube and impingement on a very small hole in
the wall of the chamber in which the filament is located. A rough
pump removes most of the gas between the tube and hole and the
particles passing through the hole are directed at the heated
filament. An ion lens positioned in the chamber adjacent the heated
filament generates an electric field which withdraws and focuses
the ions from the heated filament surface, and a slit aperture
defines the particle ion beam which is directed to a conventional
mass analyzer. Each contaminant particulate generates one short
burst of the ions by surface ionization, and the number of ions per
burst is a measure of the amount of the particular contaminant per
particulate as measured by a suitable electron multiplier at the
output of the mass analyzer. Continuous mass spectrometric analysis
is obtained with my method and apparatus. If continuous analysis is
not necessary, the gas sample can be impinged on the cold filament
for a given length of time, the gas then pumped out and the
filament heated. The integration over the time of the gas stream
impingement on the cold filament produces increased sensitivity and
does not require the rapid pumping of large amounts of the gas as
under continuous analysis conditions. The heated filament may be in
the form of a ribbon of a metal such as tungsten or rhenium. An
alternative form of the heated filament is a long heated platinum
capillary through which the gas sample is introduced into the
chamber and the impurity particle ions are produced at the heated
surface of the capillary by surface ionization and withdrawn by the
ion lens.
The features of my invention which I desire to protect herein are
pointed out with particularity in the appended claims. The
invention itself, however, both as to its organization and method
of operation, together with further objects and advantages thereof
may best be understood by reference to the following description
taken in connection with the accompanying drawings wherein like
parts in each of the several figures are identified by the same
reference character and wherein:
FIG. 1 is a diagrammatic view of a first embodiment of the ion
source chamber of my mass spectrometer in accordance with my
invention but rotated 90.degree. counterclockwise from its normal
orientation;
FIG. 2 is a top view of my mass spectrometer;
FIG. 3 is a side view, partly in section, of the mass spectrometer
illustrated in FIG. 2;
FIG. 4 is a detailed side view, partly in section, of the ion
source chamber illustrated diagrammatically in FIG. 1 but oriented
in its normal position as shown in FIG. 3;
FIG. 5 is an exploded view of the ion source and ion beam forming
electrodes depicted in FIG. 4; and
FIG. 6 is a diagrammatic view of a mass spectrometer illustrating a
second embodiment of the ion source.
Referring now to FIG. 1, there is illustrated in diagrammatic form
the essential elements of the ion source of my mass spectrometer
and which constitutes the novel aspects of my invention. The ion
source is enclosed in a chamber 10 which is partitioned to include
a gas sample inlet chamber 10a therein. Although my spectrometer is
adapted for use with various types of gases, its operation will be
described with reference to an air sample containing various
particle contaminants wherein, as defined hereinabove, the particle
may be merely molecular in size, or be the larger size particulate
matter.
The interior of chamber 10 is maintained at a relatively high
vacuum in the order of 10.sup.-5 torr and gas samle inlet chamber
10a is maintained at a rough vacuum of approximately 1 torr. Due to
the vacuum within chamber 10a, an air sample is drawn into chamber
10a through a length of small diameter metal tube 11 which passes
through an outer wall of chamber 10a. A valve 17 in tube 11
controls the air inflow. Aligned with the end of tube 11 is a very
small hole 12 in the partitioning wall of chamber 10a, and the
rough vacuum in chamber 10a removes most of the air which passes
through tube 11 and is impinged on hole 12. Some of the particles
(molecules or particulates) in the air sample pass through hole 12
and impinge on a heated filament in the form of a U-shaped metal
ribbon 13 which is heated directly by d.c. electric current to a
temperature in the range of 700.degree. to 1,700.degree. C. by
means of electrical conductors 13'. Filament 13 is fabricated of a
metal which yields a high work function, especially when heavily
oxygen covered, such as tungsten, rhenium, iridium or platinum. The
metal filament 13 is oriented such that particles passing from tube
11 through hole 12 impinge upon a major surface of the metal
filament 13 at an angle which is not critical, but is such as to
have the particles impinge at or somewhere near the center of the
filament major surface. The particles impinging on the heated
filament are evaporated as ions of the particles, i.e., the ions
are generated by surface ionization.
The ions produced as a particle impinges on the surface of filament
13 are generated as a short burst of ions for each particle, and
the number of ions per burst is directly proportional to the amount
of the particular contaminant element or compound per particle.
Thus, one molecule can generate no more than one ion and several
ions per burst are generated for each particulate. The ions are
withdrawn from the filament 13 surface by an electric field
produced by two pairs of ion beam focussing electrodes forming an
ion lens 14 which is closely spaced to filament 13 and aligned
therewith. Elements 14a and 14b of the first pair of the focussing
electrodes located closest to filament 13, are connected to a
common d.c. voltage by means of conductor 14a'. Elements 14c and
14d of the second pair of focussing electrodes are connected to two
slightly different d.c. voltages, for centering the ion beam due to
any system misalignment, by means of conductors 14c' and 14d'. A
pair of ion beam defining slits 15 for defining the width of the
ion beam directed toward a mass analyzer are positioned on the
opposite side of the ion lens 14 from filament 13 and are aligned
with both the filament and ion lens. The two slits 15a, 15b, are at
ground potential, and the slit 15a closer to the ion lens 14 is
wider than the slit 15b which is closer to the mass analyzer. The
width of the ion beam, as determined by defining slits 15 is one of
the primary characteristics in determining the resolution of a
magnetic sector mass analyzer. The short burst of ions after
passing through defining slits 15 enters a mass analyzer 30 which,
as one example, is a conventional small, portable, 90.degree.
sector, magnetic deflection-type analyzer, and which functions to
separate the ions according to their mass, the analyzer being
controlled for selecting the ions of the particular element or
compound in the gas (air) sample sought to be analyzed. The output
of the mass analyzer is coupled to an ion detector in the form of a
high gain electron multiplier for sensing the particular ions being
analyzed.
The ions produced by the surface ionization have only thermal
energy and thus only a simple mass analyzer is required for mass
analysis, that is, an energy analyzer is not required in my
spectrometer. The success of my particular method for analysis of
impurities in the gas depends to a great extent on the presence of
oxygen in the sample. The oxygen in the air sample is adsorbed on
the heated filament 13 and increases its work function. The higher
the oxygen pressure and the lower the temperature, the greater the
work function and hence, the greater the ionization efficiency.
However, the rate of vaporization and emission of ions from the
filament surface decreases with decreasing temperature so that a
compromise must be made between the efficiency of ionization and
rate of emission. The background of undesired ions also changes
with temperature and is a consideration when choosing the optimum
filament temperature. Various metallic elements including alkali
metals, alkaline earths and rare earths such as Mg, Al, Pb, Bi, Cu,
Nb, Zr, Ti, Cr, Mn, Fe and Ni among others and metallic compounds
of these elements such as LiCO.sub.3, KNO.sub.3, CrO.sub.3,
BiCO.sub.3 and CsNO.sub.3 as well as organic compounds such as
ethanol, toluene, aniline and acetone having ionization potentials
below 9 electron volts can be ionized and detected with my
spectrometer. The common components of air have high ionization
potentials (N.sub.2 = 15.5 eV, O.sub.2 = 12.2 eV, Ar = 15.7 eV) and
therefore have very little probability of being ionized. The
background due to undesired organic compounds existing in chamber
10 due to any number of reasons may be significant and in order to
reduce such background, a liquid nitrogen surface adjacent the ion
source is a desirable feature. For this purpose, a liquid nitrogen
cooled plate 16 in the shape of a toroid is located at one end of
chamber 10 adjacent filament 13 for reducing the background by a
factor of 3 to 10. The nitrogen is supplied to plate 16 by means of
inlet tube 22. Complete cooling of the entire inner surface of
housing 10 could be possible for further reduction of the
background, but would be expensive and present difficulties in
fabrication. A viewing port 18 may be utilized at the end of
chamber 10 adjacent filament 13 fo purposes of viewing the filament
and the surrounding elements.
Referring now to FIGS. 2 and 3, there are respectively shown top
and side views of my mass spectrometer and illustrate all of the
components except for the electrical power supply, rough pump which
develops the rough vacuum in chamber 10a and diffusion pump which
develops the high vacuum in chamber 10. The chamber 10 containing
the ion source is a thin walled device and utilizes heavy flanges
for obtaining sufficient pressure on copper gaskets for vacuum
sealing purposes. A pair of first flanges 20 are located along the
entire side of the chamber in which the viewing port 18 is located.
The inlet tube 22 for supplying the liquid nitrogen to the toroidal
plate member 16 within chamber 10 passes through outer flange 20
and is welded thereto. The nitrogen may be poured directly into
tube 22, or via a suitable means such as a funnel 23 as
illustrated. Chamber 10, and all of the flanges and tubes described
herein are fabricated of a metal which typically is a stainless
steel. A short length of tube 19 passes through an opening in the
top wall 10c of chamber 10 and the interior of such tube forms the
air sample inlet chamber 10a. Tube 19 is welded to the top wall 10c
of chamber 10 and the outer end of the tube is provided with a
first flange which is sealed to a second flange forming a second
pair of flanges 25. A tube 24 is welded to the second flange 25 and
the other end of tube 24 is connected to the rough pump (not shown)
which may be of the mechanical vacuum type and which establishes
the rough vacuum of approximately 1 torr in the gas sample inlet
chamber 10a. Gas sample inlet tube 11 is also connected to second
flange 25 for passage into the interior of inlet chamber 10a. Tube
26 passes through an opening in a side wall of chamber 10 and is
welded thereto. The outer end of tube 26 is provided with a first
flange which is sealed to a second flange forming a third pair of
flanges 27. A tube 36 is welded to the second flange 27 and the
other end of tube 36 is connected to a diffusion pump (not shown)
or other suitable high vacuum generating pump for developing the
vacuum in chamber 10 around the ion source of approximately
10.sup..sup.-5 torr. A third tube 28 passes through an opening in,
and is welded to, the side wall 10b of chamber 10 opposite the side
wall defined by flanges 20. The outer end of tube 28 is provided
with a first flange sealed to a second flange forming a fourth pair
of flanges 29. Tube 28 provides the exit passage for the ions from
chamber 10.
The input end of the mass analyzer designated as a whole by numeral
30 is connected to the second flange 29. Mass analyzer 30 is of the
conventional magnetic type and consists of a 90.degree. sector
fabricated as a 90.degree. stainless steel elbow 31 and includes an
entrance slit for the ion beam which enters through passage 28 and
an aligned collector slit at the analyzer output. To achieve the
high sensitivity desired in my spectrometer, an electron multiplier
32 is used as the ion detector and consists of a conventional 10
stage electron multiplier having a gain of approximately 10.sup.7.
The secondary emission electron multiplier permits the signal level
to be raised to a point at which a low output load resistance may
be used to obtain short response times to thereby make it possible
to display the spectrometer output on an oscilloscope. The short
response time permits detection of the ion bursts representing the
contaminant particles that are spaced apart by intervals as short
as microseconds. The duration of an ion burst is primarily a
function of the filament temperature and may be in a range from
microseconds to minutes. The output current of the electron
multiplier can be read by a suitable device such as an electrometer
which is capable of reading in the order of 10.sup..sup.-13
amperes.
Insulated electrical conductors 13' and 14a', 14c', 14d' which
respectively supply the d.c. power to filament 13 and the elements
of the ion lens 14, pass through a bottom wall 10d of chamber 10
within fourth tube 33 which passes through an opening in such
bottom wall and is welded thereto. The outer end of tube 33 is
provided with a first flange sealed to a second flange forming a
fifth pair of flanges 34. A suitable means 37 for sealing the
conductors feedthrough in the second flange 34 is provided, such as
a glass seal or potting compound formed on the outer surface of
second flange 34. The remote ends of the conductors 13', 14a',
14c', 14d' are connected to the d.c. power supply (not shown).
Referring now to FIG. 4, there is shown a detailed view of the ion
source chamber 10, and in particular, illustrates the manner in
which the ion source 13, ion beam lens 14 and ion beam defining
slits 15 are retained within chamber 10 in alignment with each
other and with tube 28 through which the ion beam passes enroute to
the mass analyzer 30. The side 10b of chamber 10 through which tube
28 passes, serves as a base for supporting an integral filament 13,
ion lens 14 and slits 15 structure. Four ceramic electrically
nonconductive posts 41 have first ends closely fitted into holes in
an annular member 40 rigidly connected to chamber side wall 10b.
Two or more screws pass through slit plate 15a and into member 40
to rigidly fix posts 41 within member 40 and thereby provide the
support for each of the ion source and beam focussing and defining
elements 13, 14 and 15. Only two of the posts 41 are illustrated
since this portion of the drawing is in section through the center
of chamber 10. The four ceramic posts 41 are each provided with
four cylindrical insulating spacers for separating the adjacent
elements of the ion source and ion beam focussing and defining
means from each other. Ion beam defining slits 15 comprise two
rectangular metal plates 15a and 15b generally maintained at ground
potential and with a slit in each plate of length approximaely
equal to the length of filament 13. Plates 15a and 15b are parallel
to each other and to filament 13 and the slits are aligned with
filament 13. In a typical application, the slit 15b disposed
furthest from filament 13 has a width of 0.010 inch, and the other
slit 15a is of 0.040 inch width. The narrower width beam defining
slit 15b is preferably rigidly fastened to a major surface of the
annular member 40 in any convenient manner such as by means of two
or more screws passing through plate 15b into member 40, or by
being spot welded thereto. The beam defining slit plates 15a and
15b are each provided with four holes through which the four
ceramic posts 41 pass for aligning such elements with the ion beam
focussing electrodes 14a, 14b, 14c and 14d and with filament 13.
Each of the ion focussing electrodes 14a-d is provided with two
holes through which two of the ceramic posts pass. The four
focussing electrodes form two separate electrostatic ion beam
focussing members for focussing the ions to a fine line beam, the
first pair 14a and 14b being connected to a common voltage as
described hereinabove. Each of the electrodes includes a
semicircular portion oriented parallel to the slit plates 15 and
filament 13 and through which the two holes are formed, and a
rectangular portion normal to the semicircular portion and which
primarily determines the ion beam focussing function. The spacings
between the rectangular portions of each pair of electrodes (14a,
14b) and (14c, 14d) are aligned with the slits in plates 15a, 15b
and with filament 13. A circular electrically nonconductive support
member 42 is spaced from the ion beam focussing electrodes 14a and
14b by means of the cylindrical spacers on the ceramic posts 41 and
forms the support and aligning member for filament 13. The four
holes are also formed through circular support member 42 through
which the ceramic posts 41 are installed. In addition, a large hole
which preferably is of rectangular shape is formed through the
center of member 42 for permitting viewing of filament 13 through
viewing port 18. Finally, two pairs of other holes are formed
through support member 42 and a first pair of screws passes through
a first pair of ceramic spacers 43 for rigidly securing a first
electrically conductive plate member 44 in a predetermined
orientation parallel to support member 42 and filament 13. In like
manner, a second pair of screws passes through a second pair of
ceramic spacers for securing a second plate member in a
predetermined orientation coplanar with the first plate member 44
(not shown since they are directly behind the first pairs of
screws, spacers and plate member as viewed in FIG. 4). These two
plate members 44 are each of rectangular shape and equally spaced
apart along a long edge thereof, the orientation of plate members
44 being such that the spacing between them is aligned with and
approximately equal to the width of the large rectangular centrally
located hole in member 42. The conductors 13' which supply the D.C.
power to filament 13 are attached to the major surfaces of plate
member 44 adjacent support member 42. A pair of short L-shaped
electrical conductors 46 each has a first leg thereof rigidly
attached to the opposite major surface of plate members 44 along
lines adjacent the near edges of the two plate members 44 and each
second leg of the L-shaped conductors 46 projects toward the other
plate member 44. The ribbon filament 13 is of U-shape and has its
outer two legs rigidly attached along the second legs of the
L-shaped members 46. Obviously, other means can be utilized for
supporting the ion source in chamber 10. Thus, ribbon filament 13
is retained in fixed alignment with the ion lens 14 and beam
defining slits 15 by means of the hereinabove described structure,
and the filament can be viewed during operation of my spectrometer
by peering through viewing port 18. The viewing port 18 is a small
glass plate which is sealed to an iron-nickel-cobalt alloy tube 47
that is conventionally employed for providing viewing ports in
vacuum systems. The alloy tube 47 is welded to the outer flange
20.
FIG. 4 also indicates the form of gas sample inlet chamber 10a. In
one specific embodiment, gas sample inlet tube 11 is of 1/16-inch
inner diameter but reduced at the entrance for obtaining a gas
sample flow rate of one cubic centimeter per second, and hole 12 is
of 0.002-inch diameter. Tube 19 which is provided with flange 25 at
the outer end thereof, is provided with an inner end wall 19a
through which hole 12 is formed, this end wall preferably being
normal to the path traversed by the particles issuing from tube
11.
Referring now in particular to FIG. 5, there is shown an exploded
view of the orientation of the ribbon filament 13, the ion beam
focussing electrodes 14a-d, and the ion beam defining slits 15a and
15b with the holes therethrough for the ceramic posts 41. The
direction of the particles which pass through the small hole 12 in
the gas sample inlet chamber 10a and impinge upon filament 13, and
the subsequent ion path are illustrated by the lines with the
arrowheads.
A second embodiment of the ion source is illustrated in FIG. 6
wherein a capillary tube 60, fabricated of a metal such as platinum
which can be heated in air without oxidizing, has a first end
disposed outside the top wall of the apparatus and the remainder is
located within a first chamber 61. Tube 60 is heated by means of
electrical conductors connected to a suitable D.C. power source
(not shown) and the gas sample is supplied to the first end of the
capillary tube 60 to cause surface ionization of the particles in
such gas sample which are emitted from the inner surface of the
tube 60 and withdrawn therefrom by a first slit 66 maintained at a
fixed D.C. voltage. Slit 66 also provides a means for separating
the ions from the gaseous medium within chamber 61 and thereby
allows only a small flow of the gaseous medium into the adjoining
chamber 62 in which are retained the ion lens 14 and the beam
defining slits 15. The mass analyzer 30 and ion detector 32 may be
connected by means of a suitable tubing to the output of chamber 62
as in the case of the FIG. 1 embodiment, or alternatively, as
illustrated in FIG. 6, the mass analyzer and detector may be
contained in a third chamber 63 which is interconnected with the
output of chamber 62 by means of the narrower of the beam defining
slits 15. In the case of the FIG. 6 embodiment wherein the three
chambers 61, 62 and 63 are within one housing, each chamber is
provided with a separate pump for maintaining the inside of such
particular chamber at a predetermined low gas pressure level. Thus,
a first stage pump is connected to chamber 61 for maintaining such
chamber at a pressure level of approximately 1 torr, a second stage
pump is connected to chamber 62 for maintaining such chamber at a
pressure level of approximately 10.sup..sup.-3 torr, and a third
stage pump is connected to chamber 63 for maintaining such chamber
at a pressure of approximatey 10.sup..sup.-5 torr.
The process by which the specific particles in the gaseous medium
being sampled are ionized is the same in both the FIGS. 1 and 6 ion
source embodiments and results from surface ionization by impaction
of the particles (molecules or particulate matter) on a heated
electrode which may be in the form of a U-shaped ribbon or
capillary tube. The advantages of my method and apparatus over
conventional mass spectrometric analysis are (1) an increase in
sensitivity because it does not ionize normal gases in air or the
major components of the gaseous medium, (2) the method of sample
introduction does not filter out the particles which are to be
analyzed under a continuous sampling, (3) analyzes particles
including particulate matter as to the number of particles per
volume of gas sample and the amounts of the impurity (i.e., number
of molecules) per particulate, and (4) provides for continuous
analysis of particles in a gaseous medium wherein the particles
have moderate-to-low ionization potential less than approximately 9
electron volts and includes various elements and compounds.
Another advantage of my method and apparatus for the analysis of
impurities in gaseous media is that in the case wherein continuous
analysis is not required, an even greater sensitivity of mass
spectrometric analysis may often be obtained by an integration
technique which avoids the problem of rapid pumping of large
amounts of the gas that is required for the analysis on the
continuous basis. In the noncontinuous analysis technique, the gas
stream is impinged on the cold filament 13 for a given length of
time over which the integration is to be made, then the gas sample
input flow is reduced, or completely stopped, and the pressure in
chamber 10 decreases to about 10.sup..sup.-5 torr, and finally,
filament 13 is heated to cause surface ionization of the particles
which had impinged thereon. This integration technique can lead to
increased mass spectrometric analysis sensitivity since a greater
number of the particles have collected on the filament over the
integration period and also permits the use of smaller pumps since
the gas sample need not be rapidly pumped out of chamber 10 but is
only pumped down to 10.sup..sup.-5 torr after the integration time
over which the gas stream has impinged on the cold filament.
The power supplied to the ion source (filament 13 or capillary tube
60) is adjusted to obtain the desired operating temperature in the
range of 700.degree. to 1,700.degree. C. which is determined by the
particular contaminant particles to be ionized. The voltages
applied to the ion lens 14 are adjusted for obtaining both the
desired fine line beam and a maximum ion current. The rate of
particle impingement on the filament for a given particle density
in the gas sample can be improved by increasing the pumping speeds
so that a greater flow of the gas sample can be maintained through
tube 11 in the FIG. 1 embodiment or through the capillary 60 in the
FIG. 6 embodiment. The background which is of a low level is due
primarily to contamination of metal parts adjacent the filament and
can be even further reduced by a periodic heating of such parts so
as to clean them. The background due to organic compounds may be
reduced to a low level by baking the system to approximately
400.degree. C., the longer the bakeout period, the greater the
reduction in partial pressure of organic compounds. The organic
compounds are also trapped directly at their source by utilizing
the liquid nitrogen surface 16 described hereinabove with reference
to FIG. 1.
From the foregoing description, it can be appreciated that my
invention makes available a new method and apparatus for
spectrometric analysis of impurities including particulates in the
gaseous medium which is especially well adapted for providing a
high sensitivity since it does not ionize normal gas components and
it can be utilized for continuous analysis or for increased
sensitivity by integrating over a large volume of the gaseous
medium. Having described two particular embodiments of my
invention, it should be obvious by those skilled in the art that
various changes in form and detail such as in the structure of the
filament upon which the contaminant particles are impinged and the
use of other well known ion beam focussing and beam defining
techniques and the use of other conventional mass analyzers and ion
detectors may be made without departing from the scope of my
invention as defined by the following claims.
* * * * *