All mass spectrometers consist of:

A source of ions A mass analyser (or mass separator) A means of detecting ions

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS

Also called Thermal Ionisation

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS
Also called Electron Impact Ionisation

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS

Ion sources
Surface Ionisation Plasma Ionisation Electron Ionisation Secondary-Ion RIMS

Resonant (photo)ionisation

Other ion sources

(not generally used for isotope ratio measurements) Glow Discharge Spark Source Electrospray Matrix-Assisted Laser Desorption Ionization (MALDI) Field Ionisation / Field Desorption Chemical Ionisation Fast Atom Bombardment (FAB) Ionisation and no doubt many more

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform

r = mv/qB

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform
Penning Trap

Mass Analysers
Magnetic Sector Quadrupole Time-of-Flight (TOF) Fourier Transform
Penning Trap Orbitrap

Detection
Faraday Cup Secondary Electron Multiplier Daly Detector Gas Ionisation

Detection
Faraday Cup Secondary Electron Multiplier Daly Detector Gas Ionisation

Detection
Faraday Cup Secondary Electron Multiplier Daly Detector Gas Ionisation

Detection
Faraday Cup Secondary Electron Multiplier Daly Detector Gas Ionisation
Energy and Z resolution

Finnigan Triton
Thermal (surface) ionisation Magnetic Sector, single focussing Faraday, SEM, or Channeltron detectors

Finnigan Neptune
Inductively-coupled plasma source Magnetic Sector, double focussing Faraday, SEM, or Channeltron detectors

10

IMS 1270
Secondary-Ion Source Magnetic Sector, double focussing Faraday, or SEM

Shrimp RG
Secondary-Ion Source Magnetic Sector, double focussing Reverse Geometry Faraday, or SEM

11

MegaSIMS AMS (of sorts)

Secondary-Ion Source Magnetic Sector, double focussing Faraday, SEM

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Charge and current

Current: amp, A Charge: coulomb, C, equal to 1 amp for 1 second Charge on the electron, e = 1.6 1019 C Hence, number of electrons (or singly-charged ions) per second for current I is, counts per second, cps = I/e

Electrostatic elds and potentials

Charges give rise to the electrostatic eld, E. For example, the eld due to a point positive charge has magnitude 1/r2. A charge, q, in an electrostatic eld experiences a force, F, given by F = qE Newton: work = force distance traveled in the direction of the force. The work required to move a charge between two xed points in an electrostatic eld is independent of the path taken. Such a eld is called a conservative eld. We call the work required to move unit charge from A and B the electrostatic potential dierence, V , between points A and B. V = W/q, where W is the work. With W in joules (J) and q in coulombs, V is in volts. The electrostatic potential in a volume of space completely denes the electrostatic eld there. The direction of the eld is perpendicular to lines of equipotential and is exactly analogous to the line of steepest descent being perpendicular to contour (equialtitude) lines.
2

. . . more electrostatic elds and potentials

Note: the zero of potential is arbitrary. In practice it is often taken to be the potential of the earth. A perfect electrical conductor is an equipotential. Why? A free charge will accelerate in the direction of the electrostatic eld (F = ma). Regardless of the details of the (possibly complex) arrangement of elds, the kinetic energy a charged particle gains traveling from A to B is qV . If the particle is initially at rest we have 1 KE = mv 2 = qV 2 The joule is an inconveniently large unit of energy to describe energies of individual ions or electrons. Instead, we often use the electron-volt (eV) dened as the energy required to move one electron through a potential dierence of 1 volt. 1 eV 1.61019 joules. The usual prexes apply: keV, MeV . . . Tip: use mks units (metre, kilogram, second, [amp]) energy in joules (J), charge in coulombs (C), electrostatic potential in volts (V).

Example
1. A 6Li+ ion, initially at rest, is accelerated through a potential dierence of 10 kV. What is its nal (a) kinetic energy in electron-volts (b) kinetic energy in joules (c) velocity. (Electronic charge = 1.6 1019 C, mass of proton and neutron = 1.7 1027 kg) (a) 10 keV (b) (1.6 1019 C) (104 V) = 1.6 1015 joules (c) Using KE = 1 mv 2 2 v 2 = 2 1.6 1015/(6 1.7 1027) m2s2 v = 5.6 105 ms1

2. What about the same problem applied to an electron? Electronic mass = 9.11031 kg. (a) Same (b) Same (c) Using KE = 1 mv 2 2 v 2 = 2 1.6 1015/(9.1 1031) m2s2 v = 5.9 107 ms1 (Relativistic treatment gives v = 5.8 107 ms1).

Some applications of electrostatic elds in mass spectrometry

Acceleration of ions.

Beam steering. The eld between (innite) parallel plates is uniform and r to plates: E = V /d. Electrostatic quadrupole lens (e.g. Neptunes zoom quad) eld is linear in x and y: Ex = V x/a2, Ey = V y/a2, where 2a is the aperture of the lens Round and rectangular lenses. Cylindrical ESA: eld is radial and 1/r, Er = V r ln(r2/r1) V 1 1/r2 )

Spherical ESA: eld is radial and 1/r2, Er =

r2(1/r

2r1 d V2 V1

-V/2 E=V/d +V/2

E V2 V1 2r1

2r2 2r2 E = (V2-V1) / {r ln(r2/r1) } E = (V2-V1) / {r (1/r1 - 1/r2) }

2

Ex = 2V0 x/ a2 Ey = -2V0 y/ a2

Electrostatic analysers (ESAs)

Consider a cylindrical or spherical ESA and an ion trajectory which passes exactly mid-way between the plates. This is sometime called the central, median, or axial trajectory. The electrostatic eld E is constant along the ions path so the trajectory is circular. Applying the formulae F = ma (Newtons third law) and a = v 2/r (acceleration due to motion in a circle) we see that qE = mv 2/r

ESAs continued
The radius of the trajectory, r, is proportional to mv 2/q, the ions kinetic energy to charge ratio. Electrostatic analysers are therefore energy analysers.

Momentum
Momentum, p = mv. For ions, charge q, accelerated from rest though a potential dierence V , 1 2 mv = qV 2 eliminating v gives, p2 = 2mqV Therefore, ions of dierent mass but the same kinetic energy (i.e. the same accelerating potential) have momentum m. Why do we care about momentum?

Magnetic elds
Motion of charged particles in magnetic elds: F = qv B. The force acts in a plane perpendicular to the plane dened by the directions of v and B. Since the force is always perpendicular to the velocity, the eld does no work on the charge, the kinetic energy is unaected and the trajectory is helical if B is homogenous. In the special case where v and B are at right angles, F = qvB and the trajectory is circular if B is homogenous.. Note: in standard SI units (mks system) B is in tesla: 1 T = 104 gauss. Earths eld: 0.250.65 gauss. Radius, r, of circular trajectory follows directly from F = ma and F = qvB. For circular motion, a = v 2/r. Eliminating F and a gives, mv 2/r = qvB r = p/qB Hence the radius is proportional to the momentum to charge ratio. Magnetic elds are momentum analysers.

10

Magnetic elds continued

If ions are constrained (e.g. by slits) to follow a particular radius in order to be detected, a given mass will be transmitted when p B = qr 2mqV = qr 1 2mV = r q

Remember: V is the potential dierence used to accelerate the ion, m is the mass and q is the charge. If V and r are xed, B m/q.

11

Mass calibration
We have seen that, for ions to follow a circular path of given radius, the mass vs eld relationship in a mass spectrometer is of the form B m/q. In an ideal system, this would be the precise form of the mass calibration curve. In practice, the eld is not perfectly homogeneous. For example, the eld cannot sharply drop to zero at the pole boundaries since this is not allowed by the governing equations (Maxwells equations). Also, eld control is imperfect since the eld is only measured in one small ( cm) region, not over the entire length of the magnet. Finally, hysteresis ensures that the inhomogeneity will be dependent on the magnetic history of the poles. Small and dicult to predict deviations from the ideal mass calibration curve are therefore inevitable. The mass calibration must be determined experimentally with known masses (ions). Because of the hysteresis and temperature drift of the eld sensor, the mass calibration should be checked (i.e. peaks centred) frequently.

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Field control

B Imag

Electromagnet Coils B
Vhall B

Field (hall) probe

Imag (Vdac - Vhall)

+ Vdac
out

Vout (Vdac - Vhall) Power Amplifier

Differential Amplifier

DAC
18 bits

Digital to analogue converter

Combining the relationships in the gure gives B Vdac.

13

Geometric optics
We only need to know the positions of the principal foci (F and F) and the focal length, f.
x z y

Thin Lens

Governing equation: p' p'' = f

Thick Lens

F'

F''

F'

F''

p'

p''

p'

p''

Image magnication is f /p. The term stigmatic is used to mean the simultaneous focusing in both the xz and yz planes.

Focusing by magnetic sectors

The same thick-lens equations apply. The bend in the optic axis means that image and object spaces have separate coordinate systems. f = r/ sin . F and F are a distance f cos from the pole boundaries.

Focusing by magnetic sectors continued

Mass dispersion: If the relative mass dierence between two ions is m/m ( 1)

and they are separated a distance d in the collector slit plane, the mass dispersion of the spectrometer is md/m. The mass dispersion is constant, that is, independent of mass.

Stigmatic Magnets
Note: in most modern instruments, pole boundaries are often not normal to the beam path. Non-normal entry and exit strongly aects the focal properties in the radial plane (as shown) but also in the axial plane. Axial focusing arises because of the combinded eect of curvature of the eld near the boundaries plus the non-normal indicence. By this means, magnets can be stigmatically focusing. The diagram shows exactly twice the image/object distances, relative to normal incidence, at equal entry/exit pole angles of 1 sin1(4/5) = 26.6. 2

Focusing by electrostatic elds

Both spherical and cylindrical ESAs show similar focusing properties to magnetic sectors. For a cylindrical sector, the formulae are: f = r/{ 2 sin( 2)} and distance from plate boundary to the principal foci given by f cos( 2). Spherical ESAs are stigmatically focusing: f = r/ sin with principal foci f cos from the plate boundary.

Double focusing instruments

The term double focusing is normally used to mean simultaneous spatial (or angular) focusing and energy focusing. That is, in the focal plane (collector slit) ions of all divergence angles and kinetic energies at the source slit are brought together. In practice only a small range of angles and energies can be accurately focused.
Magnetic Sector Energy Dispersed Focus

Spherical ESA

Source

Red and blue ions have the same mass but different energies. Red have 10% more energy than blue

Collector

Note that, as shown in the gure, the energies are only refocused in one plane; that of the collector slit. In this plane the instrument is said to be focusing achromatically (by analogy with light optics). A fully achromatic instrument is possible (e.g. Cameca ion microprobes) by the addition of a lens between ESA and magnet.
6

Peak shape and mass resolving power

w s A B C

Collector Slit

5% full height m

s B A w

More-or-less conventional denition of mass resolving power: m/m, where m is the full peak width at 5% of full peak height.

More mass resolving power

Single slit edge (Finnigan) denition of mass resolving power: m/m, where m is measured between 5% and 95% of peak height on a single edge. Denition OK if there are only 2 masses to resolve.

95% full height

5% full height

Mass defect and nuclear binding energy

The dierence betweent the mass of the nucleus and the mass of the individual protons and neutrons (c2) is called the nuclear binding energy. All nuclei have dierent binding energies and, hence, dierent masses. This enables isobars to be resolved by high mass resolving power. The mass defect of a nuclide or molecule is simply the dierence between its mass in unied atomic mass units (u) and the sum of all its protons and neutrons. Example: Mass (u) H 1.0078 40 Ar 39.9624 16 O 15.9949 16 40 Ar O 55.9573 56 Fe 55.9349
1

Mass Defect (mu) +7.8 37.6 5.1 42.7 65.1

Therefore, the 40Ar16O molecule is 22.4 mu heavier than 56Fe. The nominal mass resolving power required to resolve these is 2500 (56/0.0224).
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Binding Energy Curve

9 O 16 8 C 12 Average binding energy per nucleon (MeV) 7 6 5 4 3 2

2 1 H 1 0 H 0

Fe 56

U 235 U 238

He 4

Li 7 Li 6

H3 He 3

30

60

90 120 150 180 Number of nucleons in nucleus

210

240

270

56Fe has one of the most tightly bound nucleus. Fission of heavier species or fusion of lighter species can release binding energy.

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Abundance Sensitivity
I0

It

1u

The abundance sensitivity (at a specied mass) is the ratio of the intensity of the tail intensity 1 mass unit away to the peak intensity. The the tail intensity is a function of residual gas pressure in the vacuum. Ions scattering o of gas molecules are deected and may be detected in the spectrum far from their correct mass. Ions lose energy if scattered therefore additional energy ltering before the detector can discriminate against scattered ions. This is achieved by an additional ESA or, in the Finnigan instruments, by a strong focusing lens, called the RPQ, which also acts as an energy lter. The RPQs transmission eciency for non-scattered ions is typically 70 80% but 5% or less for scattered ions. The abundance sensitivity sets a limit on the maximum relative abundance two isotopes (separated by 1u) at which the minor isotope can be detected.
11

07/01/2012

Zoom Optics

Zoom Optics

07/01/2012

Zoom Optics

Mass Focal Plane

Mass focal plane not perp. to axis Plane is curved, but this is usually ignored Perfectly achromatic only on axis Cups are angled to line up with beam

07/01/2012

Faraday Cup Measurements

R is not precisely known. Need gain calibration using a very stable test current generated electronically. Baseline ! 0, amp requires small input (bias) current. Doesn t matter if it is stable. Virtual amplifiers " reduces the gain calibration inaccuracy Cup factors. Very small effect. Thermal voltage (Johnson) noise across R (1 #) is Vn=(4kTR/t)1/2, t=measurement time (s). Vn=41 V s1/2 at T=300 K, R=1011 $ Long measurement: 30 min " Vn=1 V. 1 (2 #) measurement would require 2 mV beam.

Ion counting: how it s done

Discriminator rejects small pulses and outputs fixed-width (20 ns) logic-level pulses.

07/01/2012

Ion Counting: devil in the details

Not all output pulses are the same height. There is a pulse height distribution. There are also noise pulses (possibly thermal electrons). These are small and rejected by the discriminator. Some genuine, ion-induced pulses are also rejected. The ratio of the number of ions in to the counted pulses out is the yield.

More details and devils

The yield is measured frequently and can drift with time/age of the SEM. Darknoise (~baseline) can be extremely low: 1 count per minute. Near-simultaneous (<20 ns) ion arrivals cannot be distinguished. This is the deadtime of the system. If f is the true count rate, ! the deadtime and fm the measured countrate : fm" (1 - fm !) f Deadtime correction works well when fm ! << 1 Non-linearity: a countrate-dependent effect (in addition to the effect of deadtime) which must be empirically calibrated. Can be several permil per decade. Possible causes: current drawn on SEM dynodes drops their voltage, dynode heating,?

07/01/2012

Faraday vs Ion Counting

Johnson Noise: V=IR Jn=(4RkT/t)1/2 (volts) rel.Jn=(4kT/Rt)1/2/I rel.Jn (1/I) (1/Rt)1/2 Shot Noise: n=t I/e Sn=n1/2 (no. of ions) rel.Sn=(1/n)1/2 rel.Sn(1/I)1/2 (1/t)1/2

Faraday vs Ion Counting

1000 100 10 1 0.1 0.01 0.001 0.0001 0.00001 0.0001

Johnson and Shot Noise Measurement time 5 mins

Relative Noise (1 ! )

1e11 ohms Jn 1e10 ohms Jn 1e12 ohms Jn Shot Noise

0.01

100

10000

Beam Current (pA)

07/01/2012

Publications
H.E. Duckworth, R.C. Barber, and V.S. Venkatasubramanian. Mass Spectrometry 2nd ed. Cambridge (1990). A. Septier. Focusing of Charged Particles. Vols I and II. Academic Press (1967). M.E. Wieser and J.B. Schwieters. The development of multiple collector mass spectrometry for isotope ratio measurements. Int J. Mass Spectrom. (2005) 242, 97-115 J.M. Hayes and D.A. Schoeller. High precision pulse counting: liminations and optimal conditions. Anal. Chem. (1977), 49(2), 306-311. A. Montaser. Inductively coupled plasma mass spectrometry. Wiley-VCH (1998).

Chris Coath January 7, 2012 Please choose the best answer. 1. All mass spectrometers have a) an accelerating potential dierence of several megavolts b) a magnetic eld c) a quadrupole lens d) an ion detector e) Faraday cups 2. Mass spectrometers are used in a) organic chemistry b) trace element measurements c) isotope measurements d) materials science e) all of the above 3. An electrostatic eld will always a) accelerate ions in the direction of the eld b) accelerate ions in their direction of travel c) accelerate ions perpendicular to their direction of travel d) focus ions e) both (a) and (d) 4. A magnetic eld will always a) accelerate ions in the direction of the eld b) accelerate ions in their direction of travel c) accelerate ions perpendicular to their direction of travel d) accelerate ions perpendicular to the direction of the eld e) both (c) and (d) 5. A 10 keV
40

Ar2+ ion
40

b) travels at the same speed as a 10 keV c) travels faster than a 10 keV d) travels faster than a 10 keV e) none of the above 6. A 10 kV potential dierence accelerates speed is a) 89 km/s b) 9.2 m/s
40 40 +

a) travels at a speed in excess of 3 108 m/s

Ar+ ion

Ar+ ion by a factor of

Ar ion by a factor of 2
238

U+ ions from rest. Their nal

Chris Coath January 7, 2012 c) 63 km/s d) 2.8 km/s e) 84 m/s

7. A beam of ions are detected using a Faraday cup. The Faraday cup amplier has a 1012 ohm feedback resistor. If the output of the amplier is 6 volts, the ion beam current is a) 6 pA b) 60 pA c) 600 pA d) 6 nA e) 60 nA 8. The beam in question (7) is identied as 238 U+ ions. A simultaneous measurement of 234 U+ is made on the secondary-electron multiplier. Ignoring any mass-bias and given an SEM yield of 98%, a transmission eciency through the RPQ of 80%, and 234 U/238 U= 5.29 105 the count rate, in counts per second (cps), on the SEM is a) 2530 cps b) 159 cps c) 1980 cps d) 1560 cps e) 1590 cps 9. What is the greatest relative precision (1) which could be expected of the 234 U/238 U ratio measured in question (8) for a measurement taking 10 minutes? a) 64 ppm b) 0.1 ppm d) 8 e) 1 c) 25

10. The same U isotope beams in question (8) are now both measured by Faraday cup, the minor isotope beam being amplied using a 1011 ohm feedback resistor. Assuming an ambient temperature of 300 K, what relative precision (1) could be achieved in a 10 minute measurement? b) 50 c) 20 e) 1 a) 100

d) 200

Chris Coath January 7, 2012

11. What (nominal) mass resolving power is required to resolve 40 Ar4+ (mass defect -37.6 mu) from 10 B+ (mass defect +12.9 mu)? a) 0.45 b) 450 c) 1800 d) 2900 e) 2.2 12. What (nominal) mass resolving power is required to resolve from 52 Cr+ (mass defect -59.5 mu)? a)
40

Ar12 C+

b) 540 c) 2400 d) 1800 e) 420