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Quadrupole Mass
Spectrometry
Concepts

Mass Spectrometers for

Residual Gas Analysis
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Residual Gas Analysis

What does Residual Gas Analysis allow us to do?

• RGA is the examination of the molecular components present in
a vessel or evolved from a system.
It allows us to analyse, ON-LINE HAL4 EQS High Energy #8431

in REAL time: 1.1e-05

1e-05

9e-06

•
8e-06

Base Pressure Fingerprint 7e-06

7x 10-6 torr

• Leak Detection

Faraday : torr
6e-06

• Virtual Leaks / desorption

5e-06

•
4e-06

Outgassing / Bakeout Cycles 3e-06

• Pump Performance 2e-06

1% Argon

•
1e-06

Chamber contaminants 0
0 5 10 15 20 25 30 35 40 45 50

mass : amu
Cycle number 0000000

• Characterise your system and process for optimum results

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Residual Gas Analysis

Typical contaminant species present may be readily identified:

• Air leak: m/e 28 / 32 (ca. 4.5:1 ratio) confirm by the presence of

peaks at m/e 14, 16
• Water: m/e 18 confirm by m/e 17
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Residual Gas Analysis

Typical contaminant species present may be readily identified:

• Hydrocarbons: characteristic groups of peaks, typical peaks at m/e 57,

55, 45, 43
High mass peaks - back-streaming of oil or Vacuum Grease
Low mass peaks - Cleaning fluid / solvent residue
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Residual Gas Analysis

How it works 1: IONISATION – Electron Impact Ionisation (EI)

• Operation depends on the conversion of gas molecules into
charged particles, typically positive ions / fragments.
• Achieved by electron impact ionisation via thermionic emission
from a hot filament.
• A typical current is 1x10-4Amps.
• Ions extracted into the mass filter.

• n.b. Ionisation depends on the nature of the species involved.

• If a species is readily ionised it produces a higher MS signal than
one which is poorly ionised.
• Use N2 as a standard, RELATIVE SENSIVITY = 1
• c.f. Benzene = 5.9 and Helium = 0.14.
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Residual Gas Analysis

How it works 1: IONISATION – Electron Impact Ionisation (EI)

Gas molecules
Quadrupole
entrance
Electron beam aperture 0V

Source cage +3V

Positive ions
extracted into
mass filter
Filament –70V

Extractor –90V
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Residual Gas Analysis

How it works 1: IONISATION

The choice of filament material is important:

Operating
Material Comments
Temperature
Too hot for RGA use
Tungsten 2400 K
Reacts with oxygen to give CO, CO2
Too hot for RGA use
Rhenium 2300 K
Forms compounds which are insulators
Thoria Good general purpose
1900 K
(Thoria coated Iridium) Robust
Not robust enough for RGA use
LaB6 1300 K
Very brittle

Lower operating temperature = lower outgassing

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Residual Gas Analysis

How it works 1: IONISATION

It is also important to note that EI yields several types of ions:

Ion Description

Molecular The molecule with a positive charge by loss of an electron

Base The most abundant ion in the spectrum

Fragment Formed by cleavage of one or more bonds in the molecule

Rearrangement Formed by bond cleavage and atomic migration

Doubly Charged 2+ Ions from 2 electron loss steps appearing at 1/2 mass i.e. m/2

Metastable Fragmentation of ion into an ion of lower mass + a neutral particle

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Residual Gas Analysis

How it works 2: THE MASS FILTER

• The mass filter differentiates the ions produced and selects

species for detection.
• The most common form of mass filter is the Quadrupole.
• A Quadrupole is 2 pairs of parallel, equidistant metal rods
(poles) biased at equal, but opposite potentials
• These twin potentials contain fixed DC
and alternating RF components. By
varying the RF component the
resultant field produced by the rods
may be varied.
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Residual Gas Analysis

How it works 2: THE MASS FILTER

• Any ions entering the quadrupole field experience potential

differences deflecting them from their original trajectory.
• The extent of deflection of any ion entering the field is related to its
mass : charge (m/e or m/z) ratio.
• At each interval on the RF scan only one m/e ratio resonates with
the field allowing the ion to pass along the z-axis.
• All other species are deflected and neutralised by impact upon
the rods of the quadrupole
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Residual Gas Analysis

How it works 2: THE MASS FILTER

y
- (Vdc + Vrf cos t)

x 0.168
0.167 Y-Unstable X-Unstable
0.166
0.165
U Stable

.
0.164
=
V 0.163
0.162
0.161

+(Vdc + Vrf cos t) 0.16

0.67 0.68 0.69 0.7 0.71 0.72 0.73
.

4qV
2 2 = 2
 mr0
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Residual Gas Analysis

How it works 2: THE MASS FILTER -Mathieu Stability Diagrams

10
10
10
10

88
8
8
8

66
6
6

44
4
4

22
2
2

XZ 0
YZ 00
0 00 0.5
0.5 11 1.5
1.5 22 2.5
2.5 33 3.5
3.5 44 4.5
4.5
0
0 0.5
0.5 1
1 1.5
1.5 2
2 2.5
2.5 3
3 3.5
3.5 4
4 4.5
4.5

-2
-2
-2
-2

-4
-4
-4
-4
-4

-6
-6
-6
-6

-8
-8

-8
-8

-10
-10

-10
-10
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Residual Gas Analysis

How it works 3: THE DETECTOR
• Filtered ions strike the detector to result in an ion current
which is measured by a sensitive amplifier.

Two main types of Detector:

• a) The Faraday Cup – an earthed passive conducting
surface with a suppressor electrode to avoid false
measurement.
• Fast moving ions strike the cup cause a ‘shower’ of
‘secondary’ electrons. The use of the ‘cup’ rather than a
plate, allows all electrons to be collected.
• Hence, one ion arriving at the Faraday needs one
electron for neutralisation but causes several electrons
to be emitted; this provides amplification – several
electrons for each ion.
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Residual Gas Analysis

How it works 3: THE DETECTOR

• a) The Faraday Cup: Detection limits Electron suppressor

• Ion current for N2 is 10-4 amps / Torr +ve ions Electrometer

• At 10-8 torr of N2, Faraday Cup

10-8 * 10-4 = 10-12 amps

• At 10-11 torr of N2 = 10-15 amps Analyser exit

 Detection limit for conventional analogue amplifier

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Residual Gas Analysis

How it works 3: THE DETECTOR

• b) Secondary Electron Multiplier / Single Channel Electron
Multiplier (SEM / SCEM):
A surface designed to generate secondary electrons.
• The ion impacts the surface generating 2 or 3 electrons each
of which undergo further surface collisions generating more
electrons, and so on in a cascade effect.
• Power for this cascade provided by an applied voltage.
• Gain is typically 103 (102 for a channel plate)

Minimum detectable pressure

10-14 Torr to 10-13 Torr
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Residual Gas Analysis

How it works 3: THE DETECTOR

Detector Pros and Cons:

Faraday Cup :
• Lower cost
• Indestructible
• Accurate
BUT :
• Detection limit 10-11 Torr
• Measurement relatively slow near detection limit
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Residual Gas Analysis

SEM / SCEM :
• Detection limit 10-14 - 10-13 Torr with analogue detection
• Faster measurement
BUT :
• Expensive/ Expendable/ Sensitivity species dependent
• Sensitivity time / application dependent
• Typical maximum pressure of 10-5 - 10-6 Torr
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Residual Gas Analysis

Resolution :
• The ability to separate /resolve ions of different m/e ratios
• All definitions directly / indirectly relate peak width to height
• e.g.
M / M

• M at 10% peak height where M <1 a.m.u.

• i.e. For any given mass M, the peak width at 10% of the peak
height, measured from the baseline, is less than 1 amu

• This may be complicated if the mass peaks of trace species occur

in the peak tail of a major species e.g. the detection of m/e 27 or
m/e 29 in the presence of N2 at m/e 28.
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Residual Gas Analysis

Interpretation and Cracking Patterns:

• RGA does NOT interpret, data is presented as a profile of mass /

charge peaks. e.g. the RGA of Air :
HAL IV RC RGA 201 #10940
Faraday : torr
6e-06

5e-06

4e-06

3e-06

2e-06

1e-06

0
10 15 20 25 30 35 40 45 50

Cycle number 1 mass : amu

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Residual Gas Analysis

Cracking Patterns:
• Cracking arises during ionisation when the high energy
electrons used not only ionise species but fragment them. e.g.
C O + e-  (12C16O)+
12 16
Ionisation to give a peak at m/e 28
C O + e-  12C + 16O +
12 16
Cracking to give a peak at m/e 16
C O+ e-  12C+ +16O
12 16
Cracking to give a peak at m/e 12

This pattern can differentiate 12C16O from 14N2

This has peaks at m/e 28 (14N2+) and m/e 14 (14N+) from:

14
N2+ e-  (14N2) + Ionisation to give a peak at m/e 28
14
N2 + e-  14 N + 14N + Cracking to give a peak at m/e 14
(14N2) + + e-  (14N2 )++ Ionisation to give a peak at m/e 14

n.b. CO/N2 are ISOBARIC  the same mass but different composition
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Residual Gas Analysis

Interpretation and Cracking Patterns:
• Using Cracking Patterns it is possible to identify all species
• NOTE: The cracking pattern is directly related to the energy
of the electrons used i.e. Under normal conditions the Cracking pattern
is characteristic of a species

HAL IV RC RGA 201 #10940

Faraday : torr
6e-06
N2 m/e 28, 14
5e-06

4e-06

O2 m/e 32, 16
3e-06

H2O m/e 18,17 CO2 m/e 44, 28, 16

2e-06

Ar m/e 40
1e-06

0
10 15 20 25 30 35 40 45 50

Cycle number 1 mass : amu

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Residual Gas Analysis

Interpretation and Cracking Patterns:

• Cracking pattern example – Linear Hydrocarbons
• Decane (C10H22) and Butane (C4H10) show similarities – why?

Both compounds show

Clusters of Peaks at:

m/z 57
m/z 43
m/z 29

 Loss of unit of mass 14

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Residual Gas Analysis

Interpretation and Cracking Patterns:

• Cracking pattern example

• The mass 14 unit  loss of alkyl-type species CH2 i.e.

C10H22+ e-  C10H21+ +e-  CH3+, C2H5+, C3H7+, C4H9+, C5H11+ etc.

and
C4H10+ e-  C4H9+ +e-  CH3+, C2H5+, C3H7+

 FRAGMENTATION – Bond cleavage AND Ionisation.

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Residual Gas Analysis

Interpretation:
• Isotopic Abundance.
• Many species exist as several naturally occurring isotopes:

Atom Isotopes and relative abundances

12 13
Carbon C – 100, C– 1.1
14 15
Nitrogen N – 100, N – 0.4
16 18
Oxygen O - 100, O – 0.2
Fluorine Monoisotopic
35 37
Chlorine Cl – 100, Cl – 32.5
79 81
Bromine Br – 100, Br - 98
Iodine Monoisotopic
Phosphorous Monoisotopic
32 34
Sulfur S – 100, S – 4.4
28 29 30
Silicon Si – 100, Si – 5.1, Si – 3.4
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Residual Gas Analysis

Interpretation (continued):
• Isotopic Abundance eg: Sulfur isotopes in the MS of SF6

SF5+
32

32
SF3+
32
SF4+
SF2+
32

34
SF5+
34
SF3+
34
SF4+
34
SF2 +
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Residual Gas Analysis

Interpretation:
• General steps in interpretation of a Mass Spectrum.

1. Look for the Molecular Ion(s)

2. Note the general appearance of the spectrum
3. Check spectrum for peak clusters for Isotope patterns
4. Check for low-mass neutral fragment loss e.g. CH 2
5. Check for characteristic low-mass fragments
6. Compare to reference spectra
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Quadrupole Mass Spectrometers

Hiden manufactures a wide range of MS systems, all tailored

to specific customer applications. Options include:

• Mass Ranges of 50, 100, 200, 300, 510, 1000 and 2500 amu
• Ioniser options including cross-beam and Platinum
• 6mm, 9 mm or 12mm diameter rods
• Single and triple filter options
• Networking interface
• Internal cryopanel
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Hiden Residual Gas Analysers

• Rugged modular construction with precision machined radial ceramic

rod supports
• Powerful 32 bit processor with data buffering for true multi-tasking
operation
• Ion blast free for maximum sensitivity in He leak detection
• Detection to 5x10-14 Torr / PPB levels
• Bench, cart or console mounted
• Fully automated operation
• Application specific gas inlets
• Corrosive gas / oil free pumping
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Appendix 1
Interpretation and Cracking Patterns:
• Table 1a gives some of the common RGA contaminants.
Peak 1 Peak 2 Peak 3 rel
Name Formula
m/e % m/e % m/e % sens
Acetone C3H6O 43 100 58 33 15 20 3.6
Air 28 100 32 27 14 6 1.0
Ammonia NH3 17 100 16 80 15 8 1.3
Argon Ar 40 100 20 16 36 0.3 1.2
Benzene C6H6 78 100 77 19 52 16 5.9
Boron Trichloride BCl3 81 100 58 33 15 20 1.0
Carbon Dioxide CO2 44 100 16 9 14 6 1.4
Carbon Monoxide CO 28 100 12 5 16 2 1.05
Carbon Tetrafluoride CCl4 69 100 50 12 19 7 1.0
Diborane B2H6 26 100 27 97 24 90 1.0
Ethane C2H6 28 100 27 33 30 26 2.6
Fomblin Oil 69 100 20 28 16 16 1.0
Freon 12 CCl2F2 85 100 87 32 50 16 2.7
Helium He 4 100 0.14
Hydrogen H2 2 100 1 2 0.44
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Appendix 2
Interpretation and Cracking Patterns:
• Table 1b gives more common RGA contaminants.

Peak 1 Peak 2 Peak 3 rel

Name Formula
m/e % m/e % m/e % sens
Hydrogen Chloride HCl 36 100 38 32 35 17 1.6
Hydrogen Sulfide H2S 34 100 32 44 33 42 2.2
Krypton Kr 84 100 86 31 82 21 1.7
Methane CH4 16 100 15 85 14 16 1.6
Methanol CH3OH 31 100 32 67 29 65 1.8
Neon Ne 20 100 22 10 21 0.3 0.23
Nitrogen N2 28 100 14 5 29 1 1.0
Oxygen O2 32 100 16 9 0.86
Phosphine PH3 34 100 33 33 31 32 2.6
Pump Oil 57 100 55 73 43 73 1.0
Silane SiH4 30 100 31 78 29 29 1.0
Silicon Tetrafluoride SiF4 85 100 86 5 28 4 1.0
Sulfur Dioxide SO2 64 100 48 50 32 10 2.1
Water H2O 18 100 17 21 16 2 0.9
Xenon Xe 132 100 129 98 131 79 3.0