A personall perspective

ti on the
th
development
p
of q
quadrupole
p
and
time--oftime
of-flight SIMS
1969--1992
1969

The beginnings of static

static SIMS
Wediscoveredanumberofdifferentanionspeciesinthespectrum,atomicones
Wediscoveredanumberofdifferentanionspeciesinthespectrum,atomicones
likeF,,Cl
Cl orBr,but
,butinadditionmolecularclusterionslike
inadditionmolecularclusterionslikeCO
CO3,NO3 and
andSO
SO4.
Mostsurprising,however,was
Mostsurprising,
however,wastheappearanceoforganicanioncomplexeslike
theappearanceoforganicanioncomplexeslike
CH3(CH2)nCOOH withhigh
withhighintensities.
intensities.These
Theseunexpectedresultstoldusthat
unexpectedresultstoldusthat
sputteringwasmuchsofterthan
sputteringwasmuchsofterthananybodyexpected
anybodyexpectedatthattime.Itshouldbe
atthattime.Itshouldbe
possible
possibletogeneratecharacteristicmolecularsecondaryions
possibletogeneratecharacteristicmolecular
to generate characteristic molecular secondaryionsfromevenlargeror
secondary ions from
fromevenlargeror
even larger or
morefragilemolecularsurfacespeciesbyionbombardment.
morefragilemolecularsurfacespeciesbyionbombardment.Spectratakenfrom
Phys.Status
Phys.StatusSolidi
Solidi 34,169(1969).

Quotefrom:A.Benninghoven,in
Quotefrom:A.Benninghoven
,inTof
TofSIMS:
SurfaceAnalysisbyMassSpectrometry,
f
y
y
p
y,
TheHistoryofStaticSIMS
TheHistoryofStaticSIMS APersonal
Perspective,J.C.Vickerman
Perspective,J.C.
Vickerman andD.Briggs,
Eds.,2001

UHV Quadrupole
Q d
l SIMS
instrument

A.Benninghoven
A.
Benninghoven andE.
andE.Loebach
Loebach,Rev.Sci.
,Rev.Sci.Instrum
Instrum..42,49(1971).
42,49(1971).

Implications for catalysis

M.Barber,J.C.
M.Barber,J.C.Vickerman
Vickerman andJ.
andJ.Wolstenhome
Wolstenhome,FaradayTrans.,72,40(1976)
,FaradayTrans.,72,40(1976)

Recombinationmodelforsomemolecularclusters

Implications for bioanalysis (I)

Thedesorptionofundestroyed
molecularionscanbeexplainedonly
p
y
bytheassumptionofanothertypeof
secondaryionemissionprocess.Itis
assumedthatthisprocessistheresult
ofacollectiveelectronicexcitationin
an area near the surface by the
anareanearthesurfacebythe
impingingprimaryion.Inaddition,the
molecularionissupposedtobe
boundonthesurfacebyelectrostatic
forceswhichareperturbedbythis
collectiveelectronicexcitation.Inthis
waythedesorptionofan
unfragmented particlecanbe
explained.

Theappearanceofmolecularionsinthesecondaryionspectraofthe
i
l l i
i
d
l l
d
organicmoleculesinvestigatedwascompletelyunexpected.
A.Benninghoven andW.Sichtermann,Org.MassSpectrom.12,595(1977).

Implications for bioanalysis (II)

PDMS (1976) and FAB (1979)

opened
p
mass spectrometry
p
y to
biomolecules,, setting the stage
biomolecules
for MALDI and electrospray MS
in 1985.

TOF--SIMS enters the scene

TOF
A timetime-of
of--flight mass spectrometer for measurement of secondary ion
mass spectra
B. T. Chait1 and K. G. Standing
Physics Department
Department, University of Manitoba
Manitoba, Winnipeg
Winnipeg, Manitoba R3T 2N2 Canada
Received 25 March 1981.
Abstract
A timetime-of
of--flight mass spectrometer has been constructed at the University of Manitoba
Manitoba.
In this instrument, bursts of alkalialkali-metal ions of 10 ns duration strike a thin layer of
organic material deposited onto a metal backing. The secondary ions produced are
accelerated across a fixed potential 10 kV, then travel down a flight tube 1.6 m long.
Measurement of the time of flight determines the massmass-to
to--charge ratio of the ions
ions.
Mass spectra from biomolecules with masses up to 1355 Dalton have been measured
with the instrument. They exhibit significant quasimolecular ion peaks.

With competition from Germany and

USA
InMunster,Bennighoven completedaTOFSIMSImachinein1979,which
eventuallymorphedintothemodernreflectronbasedinstrumentationTOFSIMS2
C
CurrentlymarketedbyIonTOF.TheTRIFTIwasdevelopedinabout1984atEvans
l
k db
O
h
d l
di b
98
andAssociates.VGandKratos??

E.Niehuis,T.HellerandA.Benninghoven,J.Vac.Sci.Technol.A5,1243(1987).

Imaging..
Imaging

Laser Postionizaton
Postionizaton?
?

N.Winograd,"IonBeamsandLaserPostionizationforMoleculeSpecificImaging",
,
(
)
Anal.Chem. 65,622A(1993).

SIMS XIII 1992

SIMSXIII

50

number of papers

1995

1997

Brusselss
Nara

10

Mnster

20

Orlando

30

n Diego
San

40

Manchester
M

Quantification(ofstuffinSi) 70pages
Instrumentation(microbeam analysis) 100pages
DepthProfiling(ofstuffinSi) 180pages
P l
Polymersandorganics(mostlytof)
d
i (
tl t f) 50pages
50
Metals,semiconductors,geology 130pages
DynamicSIMSbioimaging 40pages
StaticSIMSrepresentedabout20%ofthetalks
p

1999

2001

year

2003

2005