U.S. patent number 3,727,047 [Application Number 05/165,067] was granted by the patent office on 1973-04-10 for time of flight mass spectrometer comprising a reflecting means which equalizes time of flight of ions having same mass to charge ratio.
This patent grant is currently assigned to Avco Corporation. Invention is credited to George Sargent Janes.
United States Patent |
3,727,047 |
Janes |
April 10, 1973 |
**Please see images for:
( Certificate of Correction ) ** |
TIME OF FLIGHT MASS SPECTROMETER COMPRISING A REFLECTING MEANS
WHICH EQUALIZES TIME OF FLIGHT OF IONS HAVING SAME MASS TO CHARGE
RATIO
Abstract
In a time of flight mass spectrometer ions accelerated from the
source are reflected by a soft reflection field toward the
detector, the magnitude and direction of the reflection field being
such as to lengthen the time of flight of ions of relatively high
initial kinetic energy more than ions of relatively low initial
kinetic energy so that ions of the same mass to charge ratio, but
of different initial velocity will have the same total time of
flight from the source to the detector. Thus, ions of a given
charge to mass ratio which enter the system at different initial
energies at a given time will all arrive at the detector at the
same time.
Inventors: |
Janes; George Sargent (Lincoln,
MA) |
Assignee: |
Avco Corporation (Cincinnati,
OH)
|
Family
ID: |
22597276 |
Appl.
No.: |
05/165,067 |
Filed: |
July 22, 1971 |
Current U.S.
Class: |
250/283;
250/287 |
Current CPC
Class: |
H01J
49/405 (20130101) |
Current International
Class: |
H01J
49/40 (20060101); H01J 49/34 (20060101); B01d
059/44 () |
Field of
Search: |
;250/41.9TF |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lawrence; James W.
Assistant Examiner: Grigsby; T. N.
Claims
What is claimed is:
1. In a time of flight mass spectrometer, the combination
comprising:
a. ion producing means for producing ions and accelerating said
ions in a predetermined direction;
b. detecting means for detecting impinging ions;
c. means defining a linear drift region providing an ion time
dispersion according to the mass to charge ratio; and
d. reflecting means including a plurality of grids for reflecting
ions toward the detecting means after passing through at least one
of said grids, said grids providing an ion reflecting and
decelerating field the direction and magnitude of which lengthens
the time of flight of ions of relatively high velocity more than
ions of relatively low velocity, whereby ions of the same mass to
charge ratio but different velocities have the same total time of
flight from the instant of injection to detection.
2. Apparatus as in claim 1 wherein said reflecting means precedes
said linear drift region.
3. Apparatus as in claim 1 wherein said linear drift region
precedes said reflecting means.
4. Apparatus as in claim 1 wherein said linear drift region is
divided into first and second portions, said first portion
preceding said reflecting means and said second portion following
said reflecting means.
5. Apparatus as in claim 3 wherein the ions move through the drift
region toward the reflecting means at substantially constant
velocity.
6. Apparatus as in claim 5 wherein the time of flight for an ion is
substantially the total time of drift between injection and
detection plus the total time of deceleration in the reflecting
means.
7. Apparatus as in claim 4 wherein the time of flight of ions is
substantially the total drift time through both said drift region
portions from injection to collection plus total time of
deceleration in the reflecting means.
8. Apparatus as in claim 4 wherein the drift path of the ions
through the second drift region portion is substantially equal in
length to the drift path through the first mentioned drift region
portion thereby shortening the overall dimension of said
spectrometer.
9. Apparatus as in claim 1 wherein said grids are planar and
positioned substantially transverse to the direction of drift
whereby the path of each ion in said reflecting field is
parabolic.
10. Apparatus as in claim 9 wherein the path of the ions entering
the reflecting means is at an angle to the grids of said reflecting
means.
11. Apparatus as in claim 1 wherein said ion producing means
includes further means for producing a beam of energy for
evaporation and ionization of a test specimen.
12. Apparatus as in claim 6 wherein the detecting means is
immediately adjacent the reflecting means whereby the drift time is
substantially the drift time from injection to the reflecting means
plus total time of deceleration in the reflecting means.
13. Apparatus as in claim 12 wherein ions drift through the drift
region along a substantially straight line and the reflecting means
decelerating field is defined by two parallel grids which are
inclined at a skew angle to the ion drift path whereby the ions
enter the deceleration field at an acute angle of incidence.
14. Apparatus as in claim 13 wherein the angle of reflection of the
ions from the reflecting means is equal to said angle of incidence,
all ions enter the reflecting means at substantially the same point
and all ions leave the reflecting means at substantially the same
point, and said detecting means is located at said point of exit of
said ions.
15. Apparatus as in claim 1 wherein said reflecting means comprises
first, second, and third parallel grids adapted to be coupled to a
source of voltage, said first and second grids providing a first
electric field and said second and third grids providing a second
electric field, said first electric field being insufficient to
reflect said ions and said second electric field being sufficient
to reflect said ions, said first and second electric fields
providing a transit time of ions therein whereby the total transit
time of ions from said ion producing means to said ion detecting
means is invarient in both first and second order variations in the
initial kinetic energy of ions produced by said ion producing
means.
16. Apparatus as in claim 15 wherein the spacing between first and
second grids being less than the spacing between said second and
third grids.
17. Apparatus as in claim 15 and additionally including a source of
voltage coupled to said third grid for preventing ions having
energy greater than a predetermined amount from re-entering said
first electric field.
18. Apparatus as in claim 1 wherein said detecting means includes
fourth planar grid means coupled to a source of voltage for
providing a voltage on said fourth grid means for preventing ions
reflected from the reflecting means and having energy less than a
predetermined amount from being detected.
19. In a method for determining the mass to charge ratio of ions by
measuring the time of flight of said ions the steps comprising:
a. accelerating bunches of said ions at intervals through a
controlled first electric field;
b. causing said bunches of accelerated ions to sequentially pass
through a field free region wherein said ions travel at a constant
velocity;
c. providing a second electric field having a direction and
magnitude for receiving and reflecting said accelerated ions;
d. causing said accelerated ions to enter said second field at an
acute angle of incidence measured between the direction of motion
of said ions and the direction of said second electric field;
e. providing a direction and magnitude of said second electric
field causing said ions to be reflected back out at an acute angle
of reflection substantially equal to the said angle of incidence
and to travel a distance within said field substantially
proportional to ion velocity upon entering said second field
whereby said ions of the same charge to mass ratio but of different
velocities have the same total time of flight; and
f. collecting and detecting said ions reflected by said second
field, whereby the total time of flight of an ion is substantially
the time of drift plus the time of reflection.
20. A method as in claim 19 in which said accelerated ions pass
through said field free drift region prior to entering said second
electric field.
21. A method as in claim 19 in which said accelerated ions pass
through said second electric field prior to entering said field
free drift region.
22. A method as in claim 20 in which said accelerated ions pass
through a second field free drift region after passing through said
second electric field and prior to said collection and detection
whereby the total time of flight of an ion is substantially the
total time of drift before and after reflection plus the time of
reflection.
23. A method as in claim 22 and in which the drift times before and
after reflection are substantially equal.
24. A method as in claim 19 and additionally including the step of
passing said accelerated ions through a third electric field for
absorbing ions having energy greater than a predetermined
amount.
25. A method as in claim 24 and additionally including the step of
passing said reflected ions through a fourth electric field
rejecting ions having energy less than a predetermined amount.
26. A method as in claim 19 wherein said second electric field is
adjusted to absorb ions having energy greater than a predetermined
amount whereby only ions of less than a predetermined energy level
are reflected, collected, and detected.
27. A method as in claim 19 wherein said collector is adjusted to
absorb ions having energy less than a predetermined amount whereby
only ions of greater than a predetermined energy level are
detected.
Description
This invention relates to mass spectrometery and more particularly
to method and apparatus for providing improved sensitivity and
resolution in a time of flight mass spectrometer.
In mass spectrometery, the time of flight technique has advantages
over position detecting techniques. The latter require expensive
and heavy magnets and do not yield information about all mass
species at each test. The time of flight spectrometers on the other
hand do not require magnetic fields and do yield information about
all mass species essentially simultaneously at each test. In these,
a charged particle is accelerated through an electric potential and
so it acquires a velocity equal to its initial velocity, due to
initial kinetic energy, plus the square root of twice the voltage
times the ratio of charge to mass. Thus, if one assumes that the
initial velocity is negligible, then the time required for the ion
or particle so accelerated to travel a fixed distance will be a
measurement of the mass to charge ratio of the particle. Assuming
that all the ions are created at the same instance of time, and
commence acceleration in the voltage field at the same instance of
time, then the lighter ions will arrive at the detector first and
heavy ions will arrive at later times. In fact, the ions arrive at
the detector in bunches spaced in time, each bunch being indicative
of mass to charge ratio. Since the charge on each ion is known,
depending upon the formula of the ion, it is then quite easy to
determine the mass represented by the bunch and so the signal
produced at the detector representative of each bunch which arrives
at the detector is indicative of the relative quantity as well as
quality of the ions. In this manner, a sample of material can be
analyzed as to the constituent elements and the relative quantities
of each constituent.
Certain difficulties are experienced with time of flight mass
spectrometers. For example, where the ions are created by the
bombardment of residual gas atoms with an electron beam of finite
size, the fact that the ions are created at different points in
space will result in different path lengths, which in turn produce
differences in transit time even for ions of the same mass to
charge ratio. This specific source of error is less pronounced
where the ions are discharged from a solid body by the action of an
electron beam or laser beam or a spark directed to the body. In
that case, the source point is well localized and so the path for
all ions is substantially the same. Another problem arises
particularly where the ions are generated from a solid material.
Such ions exhibit a wide range of initial energies as they are
emitted from the material. Thus, the ions of a given mass to charge
ratio emitted from the solid material and then accelerated through
a given potential field will have a resulting velocity which is the
sum of the initial velocity plus the velocity imparted by the
accelerating field and so high initial energy ions of the given
charge to mass ratio will transit to the detector in a shorter time
than low energy ions. This causes a degradation in the resolution
of the device.
It is one object of the present invention to provide a method and
apparatus in time of flight mass spectrometery wherein the
degradation in resolution due to varying amounts of initial
energies of ions emitted from the source is substantially
reduced.
It is another object to provide such method and apparatus suitable
for the analysis of solid materials.
It is another object to provide a time of flight mass spectrometer
of reduced overall length.
It is a further object to provide a time of flight mass
spectrometer for the analysis of solid materials in which the
initial energy of ion particles is spread substantially greater
than possible heretofore without degradation in resolution, whereby
a greater latitude is offered in the technique for vaporizing and
energizing and ionizing material from the surface of the solid
material under analysis.
These and other objects of the present invention can be achieved
with apparatus included within an evacuated envelope including a
source of ions and an ion collector wherein ions from the source
are accelerated into a drift space and from there to a soft
reflector. The reflector directs the ions to another draft space
terminating at the collector, and so the total time of flight which
is indicative of mass to charge ratio of the ions is the time of
ion drift from the source to the reflector, plus the time of
reflection, plus the time of drift from the reflector to the
detector. These three intervals are of the same order of magnitude.
An electric field causes the reflection. The direction and
magnitude of this field is such that for ions of given mass to
charge ratio, the reflection time varies directly with incident
velocity. Thus, of these ions, those which have the higher initial
energy before acceleration spend more time in the reflection area
and the total time of flight of such ions is increased. The amount
of the increase is calculated to exactly offset their higher
initial velocity due to the higher initial energies at which they
are generated from the material under analysis.
In one specific embodiment of the present invention described
herein, the drift lengths from source to reflector and reflector to
detector are substantially equal and so time of flight of ions is
obtained with apparatus which is substantially half the length of
equivalent apparatus used heretofore. This configuration of
structure not only reduces the total overall length necessary, but
permits the detector to be shielded from direct radiation from the
source. This protects the detector from fast neutral atoms,
ultraviolet light, and X-ray radiation likely to be generated at
the source. The structural features of this embodiment are
described with respect to arrangement, dimensions, and voltages.
With this embodiment, the objects of the invention are achieved in
the analysis of a range of materials. In the design, certain
compromises and approximations are made which are described. The
principles of the invention however are applicable in any time of
flight mass spectrometer regardless of the materials under analysis
and the techniques used to generate the ions and detect the
ions.
These and other aspects of the invention will be understood more
clearly in view of the following detailed description of features
of the invention taken in conjunction with the accompanying figures
in which:
FIG. 1 is a diagram illustrating the path of flight of an ion from
the source to the detector through various field regions produced
by energized grid structures and aids to understand the principle
features in the method and apparatus contemplated by the present
invention;
FIG. 2 is a plot of a family of curves for ions of a given mass to
charge ratio, each curve representing an initial energy for such
ions, versus total transit time from grid 2 to the detector as a
function of the potential V.sub.2 on grid 2. Grid 2 is the cutoff
grid which limits the time duration of the initial pulse of ions
which enter the drift space toward the reflector. The incremental
voltage .DELTA.V shown is the equivalent excess ion energy above
the initial accelerating voltage V.sub.0 present at the ion sample
source 10;
FIG. 3 is a three quarter partially broken away view of structure
incorporating the principle features and other features of the
present invention; and
FIG. 4 is a schematic representation of another embodiment wherein
the reflecting grid structure is tilted at an angle to the tube
axis in order to produce an orbit in the reflection region, and the
detector is immediately adjacent the reflection region.
A device incorporating the principle features of the present
invention is shown schematically in FIG. 1. It utilizes a standard
ion beam source denoted 10 evaporating ions from the surface of the
sample. The energy for evaporation and ionization may derive from a
laser beam or an electron beam directed to a point on the surface
of the sample. Immediately adjacent the ion source are grid 1, 2,
and 3 which act to accelerate the ions to their drift velocities
and also act as a gating mechanism to gate out extraneous ions
which may have been generated at the wrong time. This is
accomplished, for example, by pulsing grid 2 with a voltage V.sub.2
while holding the voltages applied to the source and grids 1 and 3
constant at V.sub.0, V.sub.1, and V.sub.3 respectively. The grids
1, 3, 4, and 6 are preferably set at zero potential as is the wall
structure enclosing these grids all within an evacuated envelope.
Thus, the region from grid 3 to grid 4 and the region from grid 4
to grid 6 are drift regions through which the ions move without
accelerating. There is no potential gradient in these regions.
Grids 4, 5, and 8 form an electrostatic mirror or a soft reflector.
The electrostatic fields bounded by these grids serve to decelerate
the incident ions and reaccelerate them directing them to the
detector 11. The deflected ions move at constant velocity through
the second drift region through grids 4 and 6 and pass through
grids 6 and 7 to the detector which is preferably at a relatively
high negative voltage. Electrical signals produced in the detector
reveal the nature of the ions in terms of the ion mass to charge
ratio. The amplitude and time interval of these electrical signals
with respect to the voltage pulses applied to grid 2 reveal the
mass to charge ratio of ions evaporated from the sample and the
relative numbers of these.
In the region between each pair of grids the ions path constitutes
a segment of a parabola. This is the case in the regions between
grids where the ions have a velocity component in one direction
which is constant while at the same time experiencing an
accelerating electrostatic field orthogonal thereto. This is
particularly evident in the drift region between grids 4 and 5, and
in the reflection region between grids 5 and 8.
In an idealized case in which all times of flight or transit times
other than those spent in the two drift regions between grids 3 and
4 and 4 and 6 and in the deflection region between grids 5 and 8,
can be neglected, it can be shown by analytic techniques that the
choice of design parameters is given as follows:
0 < V.sub.0
V.sub.1 < V.sub.0
V.sub.2 < V.sub.0
V.sub.5 < V.sub.7 < V.sub.0
V.sub.3 = V.sub.4 = V.sub.6 = 0
V.sub.11 < V.sub.0
V.sub.5 = 2/3 V.sub.0
E.sub.6 = 4.sqroot. 3(V.sub.0 /d.sub.4 + d.sub.8)
Among the above parameters, the V represents voltage and the
subscript is the reference number of the grid. V.sub.0 represents
voltage at the ion source 10 and E is the electric field between
grids 5 and 8.
i.e. E.sub.6 = V.sub.0 -V.sub.5 /d.sub. 6
The total transit time of an ion from the source 10 to the detector
11 is denoted .tau. and is the sum of all transit times between all
grids. If the initial excessive kinetic energy of an ion as it is
evaporated from the surface of the sample at the source 10 parallel
to the accelerating electric field is given by .DELTA.V, then the
total transit time can be expanded as a Taylor series around its
value .tau..sub.0 for .DELTA.V = 0. The Taylor series is as
follows:
The first term in the Taylor series .tau..sub.0, is the total
transit time for an ion of the given mass to charge ratio which has
zero initial excess kinetic energy and so the subsequent terms in
the series which are of progressively smaller magnitude add to the
transit time .tau..sub.0 depending upon the initial excess kinetic
energy of the ion.
The values of V.sub.5 and E above constitute two parameters which
can be used to establish a condition wherein the first two
derivatives in the above Taylor series vanish. Substituting the
preceeding appropriate values for the parameters, the following
mathematical relations are obtained:
.tau..sub.0 =(4/3)(l.sub.1 + l.sub.3) (m/2eV.sub.0).sup.1/2
.delta..tau./.delta..DELTA.V = 0; .delta..sup.2
.tau./.delta..DELTA. V.sup.2 = 0;
thus, in this case, ions of a given mass to charge ratio having a
range of initial excess kinetic energies will have transit times
that deviate only by the third order term in .DELTA.V which all
subsequent terms in the Taylor series are negligible. Thus, a close
approximation for the resolution of the instrument for ions of
different initial excess kinetic energy can be had by substitution
in the Taylor series expansion. In this case, the Taylor series
reduces to the following:
If the resolution R is defined in terms of the quantity
.DELTA..tau./.tau..sub.0 as follows:
.DELTA..tau./.tau..sub.0 .tbd. 1/2R
Then the resolution R is given by:
For example, if a resolution of 1,000 is desired then .DELTA.V/V
can be as large as plus or minus 17 per cent or 34 per cent total
span. In other words, the initial excess kinetic energy of the ion
can vary 34 per cent and still yield a resolution of 1,000. A
further step can be taken to improve resolution by intentionally
making the second term in the Taylor series slightly negative and
so that it cancels the third order term over a small range of
values.
The precise optimization of dimensions and voltages for the
arrangement of grids shown in FIG. 1 is readily done with a
computer. Such a calculation done for a typical case resulted in
the values given in Table I wherein the distance d.sub.1 -d.sub.n
are as shown and the voltages V.sub.0, V.sub.1, ---V.sub.10 are the
value present at the source and grids 1 through 10.
TABLE I
TYPICAL PARAMETERS
d.sub.1 = 5 .times. 10.sup.-.sup.3 m V.sub.2 = 1300.ltoreq.V.sub.2
< 1700 d.sub.2 = 5 .times.10.sup.-.sup.3 m V.sub.3 = 0 d.sub.3 =
5 .times. 10.sup.-.sup.3 m V.sub.4 = 0 d.sub.4 = .85m V.sub.5 =
1000v d.sub.5 = 1 .times. 10.sup.-.sup.2 m V.sub.6 = 0v d.sub.6 =
10.75.times. 10.sup.-.sup.2 m V.sub.7 = 1050v d.sub.7 = d.sub.5
V.sub.8 = 1650v d.sub.8 = .85m V.sub.10 = 3000v d.sub.9 = 5 .times.
10.sup.-.sup.3 m E.sub.6 = 60.30 volts/cm d.sub.10 = 1 .times.
10.sup.-.sup.2 m .DELTA..div.= O - 250 volts V.sub.0 = 1400v
.DELTA..tau./.tau. = .00245/4.280 = 5.7 .times. 10.sup.-.sup.4
V.sub.1 = 0v .DELTA.m/m = 1.1 .times. 10.sup.-.sup.3
Active mirror dia = 4.14 - 1.05 = 3.10 cm
A family of curves for ions of unit charge to mass ratio but of
different initial excess kinetic energy is shown in FIG. 2. These
curves are derived from the typical parameters above in Table I.
The ordinate in FIG. 2 is the transit time for an ion of unit
charge to mass ratio and the abscissa is the potential V.sub.2. It
may be noted that for affixed value of V.sub.2 at approximately
1,000 volts, the fractional spread in transit time is only about 1
part in 10.sup.4. Thus, if the initial ion pulses are short enough,
the resolution can approach 5,000. On the other hand, if grid 2 is
not used to control the length of the ion pulse, then the
resolution is about 1,000 providing V.sub.8, the potential on grid
8 of the electrostatic mirror is set at about 1,650 volts in order
to exclude ions with .DELTA.V more than 250 volts. It should be
noted that the total drift length d.sub.4 + d.sub.8 appear only in
combination as the sum. This suggests that d.sub.4 and d.sub.8 need
not be equal. If d.sub.4 <d.sub.8, it can be shown that a
smaller mirror dimension is possible although the overall
instrument length is greater.
A detailed specific embodiment of the present invention can be seen
in FIG. 3. The tube shown incorporates all the features discussed
with relation to FIGS. 1 and 2 and discloses many other features as
well. The structure is generally cylindrical in shape and many of
the parts therein are figures of revolution about the cylinder axis
22. The cylinder walls are of strength sufficient to withstand the
structural forces produced by a vacuum inside the entire space
wherein is contained the ion source and detector structures and the
electrostatic mirror. The cylinder or envelope wall is in two
sections 13 and 14 joined by a flange structure 15 and capped at
one end by the plate 16 which carries the ion source and the
detector assembly and capped at the other end by the closure 17.
The ion source assembly and detector assembly carried by the plate
16 and the electrostatic mirror assembly all within the evacuated
envelope are denoted generally by the numerals 18, 19, and 20,
respectively.
External to the structure is a laser source of radiation 21. The
laser radiation is focused by a lens 23 through a window port 24 in
wall 13. Within the envelope, the laser radiation is reflected by
mirror 26 to the surface of source plate 25. The laser has
sufficient energy to vaporize and ionize a small portion of the
sample of material mounted on the source plate 25. This illustrates
but one technique for vaporizing and ionizing material from the
source plate. Clearly, other effective techniques can be used such
as, electron beam bombardment, spark discharged, etc.
The source plate 25 in the ion source assembly 18 and the detector
plate 30 in the detector assembly 19 are positioned at one end of
the structure on opposite sides of the structure axis. The source
and detector plates are placed in individual trap door cylinder
vacuum chambers which form the ion source and detector assemblies.
These vacuum chambers denoted 31 and 32 allow the source material
and the detector to be removed for service or replaced without the
necessity of reevacuating the whole assembly. For this purpose,
vacuum pump connections 33 and 34 are provided.
Within the ion source housing 31, is the source plate 25 and three
grid structures 35, 36, and 37 which correspond to the grids 1, 2,
and 3, respectively, shown in FIG. 1. Potential is applied to the
source plate 25 through electrical connection 38 and to grid 36
through electrical connection 39 which are insulated from the
housing. The grids 35 and 37 however connect to the housing and are
at ground potential.
In the detector assembly 19, the housing 32 encloses the detector
30 insulated from the housing, grid 41 also insulated from the
housing and grid 42 connected to the housing and at ground
potential. The grids 41 and 42 correspond to grids 7 and 6,
respectively, in FIG. 1. A voltage is applied to the detector via
the terminal 43 and a voltage is applied to grid 41 via terminal
44.
In operation, a potential of about 1,400 volts is applied via
terminal 38 to the source plate 25 and a high negative voltage on
the order of -3,000 volts is applied via terminal 43 to the
detector 30. The ions created by the impinging photon energy from
the laser beam will be accelerated by the local electric field
through grid 35 which is at ground potential and will be gated by
the control voltage on grid 36. During the interval of electrical
pulses applied via the terminal 39 to the grid 36, ions will be
accelerated to a high velocity into the drift space 45.
The electrostatic mirror 20 is contained within the cylinder 14
that removably seals at flange 15 to the tube 13. This mirror
functions as the electrostatic mirror shown in FIG. 1. It repels
and deflects ions in a manner calculated to direct the ions to
detector assembly 19 and to add to the transit time of ions of high
initial kinetic energy in compensation for their high initial
energy as already described above with respect to FIG. 1. The
electrostatic mirror consists of grids 51, 52, and 53 which
correspond to the grids 4, 5, and 8 in FIG. 1. Electrical
equipotential baffle plates denoted generally 46 between the grids
52 and 53 define the region there between and insure the presence
of a uniform electric field gradient between the grids. The baffle
plates are separated by insulating standoffs denoted 47 and
uniformly matched resistors 48 are inserted between the plates to
further insure the presence of uniform electric field gradient. The
uniform field gradient between the grids 52 and 53 is necessary in
order to have precise control of the reflection time of ions which
enter the electro-static mirror at different velocities. The
aperture to the electrostatic mirror provided by a ring 49 which is
part of the flange structure 15 is at ground potential.
In operation, the ions accelerated into the drift region 45
experience no electric field in traveling through this region
between the grids 37 and 51. Likewise, the ions upon reflection
from the electrostatic mirror experience no electric field in
traveling through the drift region 50 between grid 51 and 42.
Electrostatic shielding structures (not shown) are provided
surrounding the interior of input terminals 51 and 52. Generally 51
connects electrically to grid 53 and terminal 52 provides a voltage
at one end of the matched resistors which in turn space the
potentials on the baffle plates 46 in such a manner that the
uniform gradient between grids 52 and 53 is insured.
In operation, the control grid 36 in initially biased off at a
potential somewhat in excess of that applied to grid 53, i.e.,
V.sub.2 > 1,650 volts. Under these circumstances, most of the
ions vaporized from the surface of the source 25 will not reach
grid 36 and those that do pass through grid 36 will be lost in the
system either on a wall or at grid 53. In order to select out a
time resolved group of ions, the potential of grid 36 is
temporarily lowered to some value such as 1,300 volts thereby
permitting a group of ions to pass through into the drift space 45.
This is the pulse control on grid 36. The precise selection of the
gating time is based upon consideration of resolution, mass
numbers, and sensitivity. However, for general use, gating times on
the order of 10 to 15 nanoseconds will yield excellent resolutions
characteristics for a device such as shown in FIG. 3 having an
overall length of about 1 meter. Clearly there are other methods
for gating the ion pulses. For example, the pulse interval may be
determined by the interval of a burst of radiation from the laser
21 which vaporizes the ions from the surface of the sample under
test. Alternatively, one might substitute a set (or sets) of small
deflection plates for grid 36 (or grid 2 in FIG. 1) which would
deflect ions from reaching the mirror for other than a very small
time interval.
The electric field in the electrostatic mirror will determine the
upper cutoff of the initial excess kinetic energy for the ions. For
example, in the embodiment shown in FIG. 3, grid 53 is at 1,650
volts while the source plate 25 is at 1,400 volts. Thus, any ion
with a .DELTA..nu.in excess of 250 volts will not be reflected by
the electrostatic mirror and therefore will not return to the
detector. Such ions will travel through grid 53 and be collected
there or on the walls of the tube. As the potential V.sub.2 on grid
36 is varied between, for example, 1,300 and 1,650 volts all
particles having excess energy, .DELTA..nu.from 0 to 250 will be
allowed to pass through grid 36 and will be accelerated into the
drift region 45. The electrostatic mirror 20 will in turn
decelerate and focus these high energy ions back onto the detector
which will measure the effective mass of the particle on the basis
of the total time of flight.
The operating voltages and sequences of operation of the mass
spectrometer shown in FIG. 3 and described above are suitable for
testing a wide variety of materials as the sample on the source
plate 25. The entire range of ions can be detected and measured in
this manner.
Turning next to FIG. 4, there is shown in schematic form another
embodiment of the present invention incorporating some of the
principle features. As already noted in the description of the
embodiment represented in FIGS. 1 and 3, the length of the drift
regions from the source to the electrostatic mirror and from the
mirror to the detector (denoted d.sub.4 and d.sub.8 in FIG. 1) need
not be equal. The optimum reduction in tube length is obtained when
they are equal. However, the full effect and benefit of the delay
added to the transit time for the relatively high energy ions by
the electrostatic mirror can be taken full advantage of even when
the drift lengths are not equal. Moreover, one of the drift regions
(either d.sub.4 or d.sub.8) may be eliminated, for example, the
drift region from the electrostatic mirror to the detector
(d.sub.8) can be eliminated as shown by the structure in FIG. 4.
Here the detector assembly is located immediately adjacent the
electrostatic mirror so that ions reflected by the mirror
immediately enter the detector assembly and do not pass through
another region. Of course, the overall tube length is greater, but
probably no greater than in a conventional tube (for the same
transit time) where the source and detector are at opposite ends of
the tube and facing each other.
In FIG. 4, the source of ions is from a plasma device 60. The ions
are extracted from the plasma cloud 61 in the device by the
extraction grid 62 and accelerated by the field between grid 62 and
grid 63 which is at a constant potential applied through lead 64.
The extraction grid 62 is electrically pulsed through lead 65 so
that it extracts ions from the cloud in bunches. These ions are
accelerated by the field between grid 62 and grid 63. The extracted
ions pass through grid 63 and move through the equipotential spaces
66 and 68 defined by the cylindrical extensions 67 from grid 63 and
69 from grid 71.
At the other end of the drift tube 69, the grid 71 is electrically
connected to the tube 69 and disposed at a skew angle with respect
to the axis of the tube. This grid 71 bounds an electrical field in
conjunction with the electrostatic mirror grid 72 which is parallel
therewith. The grid 71 does not bound any field with other voltage
surfaces inside the device because it is substantially shielded
from them by the drift tubes 67 and 69. These drift tubes are at
about -10 Kv.
The electrostatic mirror denoted generally by the numeral 73
consists substantially of grids 72 and 74. Grid 72 is at a high
negative potential (about -5 Kv) and grid 74 is at ground
potential. This provides a decelerating field between the grids 72
and 73. The angle that the ions turn, in leaving the drift tube 69
depends upon the skew angle of the grid 72 and 73 (denoted .alpha.)
and the field strength and dimension between these grids. The field
between grid 72 and 74 serves principally to extend the transit
time of the relatively higher velocity ions which arrive from the
drift tube as compared with the relatively slower ions. This field
also turns the ions directing them to the detector 75 located
immediately adjacent grid 72. This detector may be constructed
similar to detector 19 shown in FIG. 3.
It can be shown that all ions which enter the electrostatic mirror
at the same point and at the same angle of incidence will also
emerge from the same point at an angle equal to the angle of
incidence regardless of the mass to charge ratio of the ions.
Clearly, the electrostatic field strength in the space between
grids 72 and 74 is adjusted to add to the transit time of high
speed ions in view of the considerations described above with
respect to FIG. 1 and pertaining to the Taylor expansion equation
representing the total transit time of ions in terms of certain
voltages and initial excess energy.
The embodiments of the present invention described herein include,
with respect to FIGS. 1, 2, and 3 the best known use and
application of the invention. The invention is deemed to be the
structure as described and the method of testing described whereby
the mass to charge ratio of ions of a sample material are
determined. In these methods, electrical equipment used in
conjunction with the detector to examine the electrical signals
from the detector and determine from those electrical signals the
mass to charge ratios and the relative quantities of the ions are
not described herein. Such equipments are deemed to be well known
to those in the art and have been used in the past in conjunction
with time of flight type mass spectrometers. The spirit and scope
of the invention is set forth in the accompanying claims.
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