FIELD OF THE INVENTION
[0001] This invention generally relates to a mass spectrometer with an ion source, where
the ion source is producing an ion beam containing both carrier ions and analyte ions.
This invention specifically comprises a separation system for removing the carrier
ions from the ion beam.
BACKGROUND OF THE INVENTION
[0002] In a gas chromatography-mass spectroscopy (GC-MS) instrument, gas chromatography
is usually performed first and the resulting gas stream is then introduced into the
mass spectrometer. As a result, both the carrier gas used during gas chromatography
and the analytes become ionized and are directed as an ion beam into the mass spectrometer
detector. While the ionization cross section for the carrier gas is typically more
than ten times less than those of the analyte ions of interest, the carrier gas concentration
is orders of magnitude greater than the analytes. As a result, the carrier gas ion
concentration in the ion beam is many times more intense than the analyte ions.
[0003] One adverse consequence of this is that the electrostatic space charge effects due
to the intense carrier gas ion concentration cause the ion beam to diverge. The divergence
can be determined by the equation:

Where
Z is the distance in which the beam diameter will double
ro is the initial radius of the beam
I is the beam current
V is the beam potential
[0004] The divergent beam may cause signal loss during detection if some of the beam falls
outside the detector entrance. Another adverse consequence of the high carrier ion
concentration is detector distortion or saturation. If the concentration causes the
detector to exceed its linear range, its output will be distorted and the system may
report erroneous results. In the event that the detector becomes saturated, those
erroneous results will continue until the detector overcomes any inherent hysteresis.
[0005] One solution has been to gate the detector off during the arrival of the carrier
gas ions, but this has the disadvantage of burdening the system with additional circuitry.
Another solution has been to include an electrostatic deflection gate in the flight
region that is activated during the passage of carrier ions, thereby preventing them
from reaching the detector. This solution requires additional circuitry, additional
mechanisms, precise timing and critical placement in the flight region.
SUMMARY OF THE INVENTION
[0006] The present invention is based on the realization that it would be more advantageous
to remove the carrier gas ions from the beam as soon as possible after the ion source,
in order to prevent space charge effects and to minimize detector saturation problems.
It is the object of this invention to provide for the removal of carrier ions from
the ion beam after the ion source but before entering the mass spectrometer detector.
In accordance with the invention this is achieved by applying a magnetic or electrostatic
field to the ion beam soon after it emerges from the ion source which causes the constituents
of the ion beam to disperse according to their mass to charge ratios. Because the
amount of dispersion is related to the individual ion's mass charge ratio and the
strength of the applied magnetic or electrostatic field, the location of ions in the
plane perpendicular to the ion stream can be accurately predicted. A mechanical stop
can then be placed to block ions from the stream as desired.
BRIEF DESCRIPTION OF THE DRAWINGS
[0007]
Figure 1 shows a schematic of a mass spectrometer
Figure 2 shows a detailed view of the effects of the first magnetic field
Figure 3 shows one embodiment of the invention using three magnetic fields.
Figure 4 shows a second embodiment of the invention using two magnetic fields.
Figure 5 shows a third embodiment of the invention using three electrostatic fields.
Figure 6 shows a fourth embodiment of the invention using two electrostatic fields.
DETAILED DESCRIPTION OF THE INVENTION
[0008] Figure 1 shows a schematic of a mass spectrometer utilizing the invention. Carrier
gas containing analytes is introduced into the mass spectrometer through a sample
inlet
10. From there it travels into the ion source
20 where the gas stream is ionized. The resulting ion stream
30 may be subjected to optionally either electrostatic or magnetic fields in a first
region
40. The ion stream then passes through a separator
50 in accordance with the present invention and specific ions are blocked from the stream.
The ion stream may again be optionally subjected to additional electrostatic or magnetic
fields in a second region
60 and is then directed into a mass analyzer
70. A typical mass analyzer might consist of a quadrapole, ion trap, or time of flight
system including a detector. A vacuum system
80 keeps the main components of the mass spectrometer at negative pressure.
[0009] Figure 2 shows a diagram of the first field according to the invention, in this embodiment
a magnetic field. In Figure 2 the ion stream
30 is previously accelerated and collimated so that the ions are brought to a homogeneous
potential of 300 eV and the stream is approximately 1mm wide. In a GC-MS instrument
the carrier gas might be helium, hydrogen or nitrogen or any other typical GC carrier
gas. The beam is then subjected to a first magnetic field
90 approximately 6 mm long along its axis of travel, having a strength and polarity
of +4400 gauss, applied perpendicular to the beam. Within the magnetic field the ions
disperse, following circular paths defined by the following equation:

Where
r = the radius of the path
B = the magnetic field strength in gauss
m = the mass of a particular ion in atomic mass units
V = the potential of the particular ion
[0010] After passing through the magnetic field, the ions continue to disperse, traveling
tangentially to their previous circular paths. A particular ion's total perpendicular
deflection x
t, from the ion beam at a particular distance from the beginning of the magnetic field
is determined by the equation:

[0011] Where
xt is the total distance the ion is deflected from the beam
l is the length of the magnetic field,
L is the length the ion has traveled along the ion beam's axis of travel after the
magnetic field, and
r is the radius of the path from Equation 2
[0012] While traveling through the magnetic field, helium ions in the stream with a mass
of 4 follow a path having a 29 mm radius, hydrogen ions with a mass of 2 follow a
20 mm radius and nitrogen ions with a mass of 28 follow a 76 mm radius. Using a magnetic
field width of 6 mm, at approximately 25 mm past the magnetic field, helium diverges
approximately 6.5 mm to follow path
100 from the beam, hydrogen approximately 9.3 mm to follow path
120 and nitrogen approximately 2.4 mm to follow path
130. A physical stop
140 is constructed and placed to block particular ions and remove them from the stream.
Preferably the stop is positioned anywhere along the beam as long as the beam has
diverged enough so the stop blocks those particular ions and effectively removes them
from the stream.
[0013] Figure 3 shows an embodiment where a second magnetic field
150 of equal magnitude, reverse polarity and double the length of magnetic field
90 in the direction of ion travel is then applied to the stream causing it to reconverge.
The stream is then subjected to a third magnetic field
160 having the same magnitude and polarity as the first, in order to re-collimate and
direct the beam.
[0014] Figure 4 shows an embodiment using two magnetic fields of opposite polarity. The
ion stream
30 is accelerated and collimated so that the ions are brought to a homogeneous potential
of 300 eV and the stream is approximately 1mm wide. The first magnetic field
90 is applied, causing the ions to disperse according to Equation 2. The physical stop
140 is positioned to block the ions of interest and subsequently a second magnetic field
150 is applied, causing the beam to reconverge. Because there is no third magnetic field,
the beam will converge in an area
170 and then begin to disperse, however, the detector can be located effectively in the
region
180 around the convergence point where the beam is condensed enough to meet detection
requirements.
[0015] The actual strengths and lengths of the magnetic fields in the embodiments of figures
2, 3 and 4 may vary according to the dispersion and reconvergence required in order
to achieve acceptable detection and the available area in which to achieve separation.
The angle at which the magnetic fields are applied with respect to the direction of
the ion stream and the beam energy also may vary depending on the desired location
of the stop.
[0016] Electrostatic fields may be used with similar results. Before application of an electrostatic
separation arrangement, the ion stream is accelerated so that the ions have a homogeneous
velocity as opposed to potential. Within an electrostatic field applied perpendicular
to the ion stream's direction of travel, a particular ion follows a parabolic path
defined by the equation:

[0017] Where
x is the distance the ion is deflected from the beam,
ax is the acceleration of the ion in the direction of the field, and
t is the time the ion is present in the field
The acceleration is further defined as qE
x/m, where q is the ion's charge, E
x is the strength of the electrostatic field and m is the mass of the ion. The time
the ion is present in the field is further defined as l/v, where l is the length of
the field and v is the initial velocity of the ion along the beam's direction of travel.
Substituting these values into Equation 4 yields:

[0018] After passing through the electrostatic field, the ion continues to deflect from
the beam, traveling tangentially to its previous parabolic path. The deflection outside
the field, x
o is defined by:

where L is the length the ion has traveled along the ion beam's axis of travel after
the magnetic field, and
[0019] A is the angle of deflection from the beam outside the field
The tangent of the angle of deflection outside the field is determined by v
x/v where v
x is the velocity attained by the ion in the direction of the electrostatic field and
v is the initial velocity in the direction of travel. The velocity attained by the
ion in the direction of the electrostatic field is further defined as v
x = v
ix + a
xt where v
ix is the initial velocity in the direction of the field, a
x is the acceleration of the ion in the direction of the field and t is the time the
ion is present in the field. Assuming the initial velocity in the direction of the
field is zero (0) and using the denotation of acceleration from Equation 5 above the
tangent of A becomes (qE
xl)/(mv
y2). The total deflection from the beginning of the electrostatic field is defined by:

or

[0020] Figure 5 shows an embodiment where three electrostatic fields are applied to the
stream. In Figure 5 the ion stream
30 is previously accelerated and collimated so that the ions are brought to a homogeneous
velocity and the stream is approximately 1mm wide. The beam is then subjected to a
first electrostatic field
190 along its axis of travel, applied perpendicular to the beam.
Calculations similar to those performed for the magnetic field example above are performed
using equation 8 to determine the deflection for specific ions and the ideal location
for the stop. The physical stop
140 is constructed and placed to block particular ions and remove them from the stream.
As stated previously, the stop is positioned anywhere along the beam as long as the
beam has diverged enough so the stop blocks those particular ions and effectively
removes them from the stream.
A second electrostatic field
200 of equal magnitude, reverse polarity and double the length of electrostatic field
190 in the direction of ion travel is then applied to the stream causing it to reconverge.
The stream is then subjected to a third electrostatic field
210 having the same magnitude and polarity as the first, in order to re-collimate and
direct the beam.
Figure 6 shows an embodiment using only two electrostatic fields of opposite polarity.
The ion stream
30 is accelerated and collimated so that the ions are brought to a homogeneous velocity
and the stream is approximately 1mm wide. The first electrostatic field
190 is applied, causing the ions to disperse according to Equation 8. The physical stop
140 is positioned to block the ions of interest and subsequently a second electrostatic
field
150 is applied, causing the beam to reconverge. Because there is no third electrostatic
field, the beam will converge in an area
170 and then begin to disperse, however, the detector can be located effectively in the
region
180 around the convergence point where the beam is condensed enough to meet detection
requirements.
As with the magnetic fields embodiment, the actual strengths and lengths of the electrostatic
fields in the embodiments of figures 5 and 6 may vary according to the dispersion
and reconvergence required in order to achieve acceptable detection and the available
area in which to achieve separation. The angle at which the electrostatic fields are
applied with respect to the direction of the ion stream and the beam energy also may
vary depending on the desired location of the stop.
1. A method of separating ions from an ion beam comprising:
applying a first field at an angle to said ion beam, causing said ions to disperse
according to their mass to charge ratios;
blocking dispersed ions having a particular range of mass to charge ratios;
applying a second field to said ion beam to reverse the effects of said first field
on said ion beam; and
applying a third field to said ion beam to direct and collimate said ion beam.
2. The method of claim 1 where said ion beam comprises carrier ions and analyte ions
and said blocked ions are carrier ions.
3. The method of claim 1 wherein said first field, said second field and said third field
are a type of the group consisting of electrostatic and magnetic.
4. The method of claim 1 where said blocked ions are removed from said ion beam.
5. The method of claim 1 as utilized in a mass spectrometer having an ion source.
6. An apparatus for separating ions from an ion beam comprising:
a first field means positioned so as to apply a first field at an angle to said ion
beam causing said ions to disperse according to their mass charge ratios;
a mechanical stop located along said ion beam for blocking dispersed ions having a
particular range of mass to charge ratios;
a second field means positioned so as to apply a second field to said ion beam to
reverse the effects of said first field upon said ion beam; and
a third field means positioned so as to apply a third field to said ion beam to direct
and collimate said ion beam.
7. The apparatus of claim 6 where said ion beam comprises carrier ions and analyte ions
and said blocked ions are carrier ions.
8. The apparatus of claim 6 wherein said first field means , said second field means
and said third field means apply a type of field of the group consisting of electrostatic
and magnetic.
9. The apparatus of claim 6 where said blocked ions are removed from said ion beam.
10. The apparatus of claim 6 as utilized in a mass spectrometer having an ion source.
11. A mass spectrometer having a sample inlet, an ion source, an ion mass analyzer and
a vacuum system in combination with the apparatus of claim 6.
12. A method of separating ions from an ion beam comprising:
applying a first field at an angle to said ion beam, causing said ions to disperse
according to their mass to charge ratios;
blocking dispersed ions having a particular range of mass to charge ratios;
applying a second field to said ion beam to reverse the effects of said first field
on said ion beam, and to direct and collimate said ion beam.
13. The method of claim 12 where said ion beam comprises carrier ions and analyte ions
and said blocked ions are carrier ions.
14. The method of claim 12 wherein said first field and said second field are a type of
the group consisting of electrostatic and magnetic.
15. The method of claim 12 where said blocked ions are removed from said ion beam.
16. The method of claim 12 as utilized in a mass spectrometer having an ion source.
17. An apparatus for separating ions from an ion beam comprising:
a first field means positioned so as to apply a first field at an angle to said ion
beam causing said ions to disperse according to their mass charge ratios;
a mechanical stop located along said ion beam for blocking dispersed ions having a
particular range of mass to charge ratios;
a second field means positioned so as to apply a second field to said ion beam to
reverse the effects of said first field upon said ion beam and to direct and collimate
said ion beam.
18. The apparatus of claim 17 where said ion beam comprises carrier ions and analyte ions
and said blocked ions are carrier ions.
19. The apparatus of claim 17 wherein said first field means and said second field means
apply a type of field of the group consisting of electrostatic and magnetic.
20. The apparatus of claim 17 where said blocked ions are removed from said ion beam.
21. The apparatus of claim 17 as utilized in a mass spectrometer having an ion source.
22. A mass spectrometer having a sample inlet, an ion source, an ion mass analyzer and
a vacuum system in combination with the apparatus of claim 17.