High Resolution Surface Mass Spectrometry by TOF-SIMS - CEAC：高分辨率质谱-通过TOF-SIMS的表面

High

ResolutionSurface

MassSpectrometrybyTOF-SIMS>The

challengeofchemical

nanoanalysis>Secondary

lon

Mass

Spectrometry

-SIMS

>Analytical

application

ofTOF-SIMS>Perspectivesm

ZKeyquestionsinnanoanalysis·Identification(What?)·Localisation(Where?)·

Quantification(Howmuch?)NanotechnologyDefinition:Inat

least

one

dimension<100nmExample:Surface

mappingLateral

resolution:100

nmVolume:1×100x100nm3Amount

of

material:0.1attomolesome10.000

moleculesInformation

depth:

1

nmChemicalinformation

?·Proximityprobes(AFM,SNOM,……)·Electronemissionbasedprobes(XPS,AES,TEM,…)

·SurfacemassspectrometryExcitationby:▶Electrons▶Electricalfields→Atomprobe▶Photons→MALDI▶Ions→

Secondary

Ion

MassSpectrometry(SIMS)Ag

catalysta

:Surface

layer

b

:Bulkc:Damaged

area-

lf

(cσe)uurTheconceptofStatic

SIMSSecondaryparticles×9:ions,neutralse

:electronst<1

ps0,3

nm≠2r<120

nmhv:photonsSecondary

lon

EmissionM→X;

qX₁¹,X

₂+,X

₃,

…

…X₁+……………X₁,

X

₂,

X₃,……X……………X₁°,

X

₂⁰,

X₃°,

…

…

X°……………Transformation

probability:P(M→X

;9StaticSIMS▶Negligible

probabilityofbombardingadamagedarea→Sputtering

ofonly

a

negligiblefraction

ofthe

uppermost

monolayer

→

Reduction

ofthe

primary

ion

current

(fluence)→

Reduction

ofthe

secondary

ion

current→

Resultingconditions/requirements·

High

transformation

probabilitiesHigh

transmission

mass

spectrometer·High

sensitivity

secondary

ion

detectionSecondarypartidlesx°:lons,neutralse

:electronshv:photonsTheconceptof

StaticSIMSa:Sufaceb

:Bulkc:Damaged-surfacelayerareat<1nm<2r<120psnm-bulk(σ)0,35003500×1053.53.02.52.01.51.00.50.0m

ZIMonolayerSputteringθ(t)=θ(0).exp(-σ

.v.t)θ(t)Fractionalcoverageat

time

t

O

|Damagecrosssectionv

Primary

ionfluxdensityθ(0)Fractional

coverage

at

t=0Lifetime

t

of

one

Monolayer

θ(t)=θ(0).l/et

=1/(σ.v)Ag

catalystt(s)Ag

catalystNmlt)(Imp./Mn)MLsputteringExample:octanethiolonAu

σ=1,34.10-14cm²counts/100stime

in

sX10Massanalysersapplied

inStaticSIMS(Historicaldevelopment)MagneticsectorfieldQuadrupole(FT-ICR)Time

-of

-FlightTOF-SIMSlon

Mirrorlon

GunPulsingFocusingRasterTargetSpectrumDetectorTransportOpticsExtractorElectron

Flood

GunION-TOF

GmbHMainfeaturesofTOF-SIMS▶Parallel

massdetection▶Highmass

accuracy(1-10ppm)▶Hightransmissionfor

high

massesandat

high

mass

resolution▶Allelements

and

isotopes▶Molecular

species▶Highsensitivity(ppb,attomole)▶High

lateral

(50

nm)and

depth(1nm)resolution▶High(unlimited)mass

range▶High

mass

resolution>10000Static

SIMSOxidizedandcontaminatedmolybdenum

surface(1973)intensity

[c]×1o³16maS

5≤

[

am12.Example:PolystyreneI

Intact

Molecules(m<10,000u)(M+H)+,(M+Ag)+,(M+Na)+,

(M-H),

…("substratecationization"onlyfrom

(sub)monolayercoverages)IICharacteristicLargeFragmentslossof

functionalgroups,repeat

units,

…

.(accordingto“classical”

fragmentationrules)IIISmallOrganic

Fragmentsendgroups,fractionsof

repeatunits,m/z

sidechains,.(sufficientforidentification)MolecularInformationbyStatic

SIMScounts/chonnel0.014401460

14801500152015403×102.01.5I1.01453.3071527.3241513.2691439.259△M△MM,0.5mStatic

SIMSPhenylalanylglycine

ML

on

Ag(1981)子十十N

十dikCsD+Ag)CsA+Ag)

十CHCH₂-cD

CH-CH₂-CCH₂Cyclosporine

ACH₃cO;"CHCH₃

CH₃十sA+Nacounts

ChCHsCH[H²CH-CHd₂CoCCHCH」

CHsCsD+H)十A:R=-CH₂-CH₃D:R=-CH(CH₃)z4了CyckspotuCyclesporiMW:1202aMW:1216usA+H)C“HO,

CHCHCH^cu₃co

CH

·duCH₂

CHCH-CH₂CHCH-HCHCH」比①CHsCH₃CHCH-R;H₅CH

HCH₃①)+CH₂CH,→Al+,O,AlO+,A1O₂,

…

…→Ag*,SO₄,

…

…

…M+H+,M-H,M+Ag+,

…

…

Me,Cs+,

…

…

…Conservationofchargesigne-Examples-Al-oxideAg-sulfateM

on

AgMe-CsAlP(A1→Al+)=0,007Al-oxideP(A1→Al+)=0,7Ag-sulfateP(-SO₄

→SO₄)=0,3Me-CsP(Cs→Cs+)二1,0Transformationprobabilities(M→X;9)-Examples-P(M→M+H+)

=

0,005P(M→M+H+)

=

0l

,0001P(M→M+H+)

=

0,0000005Ag-Methionine

Ag-Bradikinin

Ag

-Mellitin(1.060amu)

(2.846amu)Systemσ/10-14cm2d/nmNi-O0,250,5Ni-H0,50,7Ni-H₂4,52,1Au

-Thiole1,31,1Ag

-Methionine4,52,3Ag

-Bradikinin20,04,9(1.060amu)Ag

-Melittin45,07,4(2.846amu)Damagecrosssections

o-Examples-Samplematerials,geometries,operationmodes▶Samplematerials

▶

Samplegeometries·Surfaces,Monolayers,Particles,Fibers,

…

…▶Operationmodes

m

aep

i

pging)····suCeramiemicons,Ssels,saGlaMet···

ylo

l,

i

s,Biopolymers,BiomoleculesesvetisAdicaersBioPolTOF-SIMS

activities▶250laboratories

are

operating

TOF-SIMS

instruments

worldwide▶BiennielInternationalSIMSConferences2019:SIMS

15(Manchester)2019:SIMS

16(Japan)(350-450

participants)BiennielEuropeanSIMSConferencesinMünster,Germany2019:SIMS

Europe

V(200-250

participants)▶MassSpectrometryMagnetic

sector

field

→Quadrupole)→(FT-ICR)→

Time-of-Flight▶

Lateral

resolution

Focused

ion

beams▶

Depth

resolution

Clusterbombardment

Lowenergy

Pl▶P(

t)ion,Cs

depositionxid→OM(Static)SIMSOptimisationNobelmetal

substratesClusterbombardmentntensitymass(u)mass

(u)Massresolution,accuracyntensityLateralresolutionExample:Photographic

Crystalslateraldistribution

of

Clon

cubic

silver

halide

crystals(Sample

provided

by

the

University

of

Antwerp,Belgium(Prof.Gijbels))lineprofileX16%-84%=50

nmsItyintensity11四0ln

te

Dt1o)nDethresolutionB

monolayer

in

Sidepth(nm)depth

/nmBconcenration/atomscmsd

layer

deposition

by

Knudsen

cell

effusion;

adeninecoverage:l:submonolayer

rangell:

monolayer

rangeIll:

multilayer

rangeInfluenceofthe

Substrate

and

the

SurfaceCoveragesputtered

from

Agcounts/s4000time

/snom.

intensiydeposition6000ClusterO→Ar→XeGa→Aun→Bi₁bombardment→SFs→CmHn→C₆oPrim

ary

ion

mass(u)Yield10~⁴-3-2MainfeaturesofTOF-SIMS▶Parallel

massdetection▶Highmass

accuracy(1-10ppm)▶Hightransmissionfor

high

massesandat

high

mass

resolution▶Allelements

and

isotopes▶Molecular

species▶Highsensitivity(ppb,attomole)▶High

lateral

(50

nm)and

depth(1nm)resolution▶High(unlimited)mass

range▶High

mass

resolution>10000massresolution(FWHM):Ti:

13119Cr:

12813Fe:

12009Cu:13849coverage(atoms/cm²):Ti:

6.1E10Cr:

8.2E09Fe:

3.1E09Cu:

2.1E10518劳5药raTraceMetalDetection

/massresolutiondata

taken

from

003_r.dat405

r475Elementdetection

limits

(atoms

/cm?)detection

limits

(atoms

/cm?)Li1E7开1E811B5E7TN6Na1F72E72E7C34K1E73F83E7*Ii2E8512F86E1Monolayer=1.5E15

atoms/cm²)▶

theerrorisestimatedtobe

within

a

factor

of

2

to

3.TOF-SIMSDetectionLimitsln

te

D

sity14depth(n

m)depth

/nmReconstructedprofile(Li,Na)Depthprofilingdepth(nm)depth

/nmBconcenration/atomscmsin

t

es

it

yintensitytio)n0CMaterialScience2D

ImagesandCrossSectionsBulk595

nmCrossection

zy

View(SampleprovidedbyProf.Martin,RWTH

Aachen,Germany)Surface

20

nmMg+Ga+Fe+Cr+Sr+Y+器Blooming

Effect

on

Polymer

Field

of

View:284x284μm²Polymer,Stabiliser,AntioxidantPolymer(PP)Melt

StabiliserAntioxidantSurfaceImaging20Lù

S‘

,00i

9'Z

,EO,OEZ'S,MgOEL‘L,eNunluein/siskjeuvəlo!ued,E9sOitLxNgczZ

。0i

6'E,UZ

OE

tLg0ù

∠‘L.eHSi*5,0~10⁶Ag*

6,4*10²NanoextractionLaser-SNMSSi5,1·10.Ag5,1·10³overlayTOF-SIMSSSiPhaseSeparationFLMAFM58:C₃

H₈

NLB-multilayersystem:Lipids:DPPC/DPPG(4:1),Protein:0.4mol%SP-CLipidProteinTOF-SIMS十Laser-SNMS110:CsH₈

N₃58:C₃

H₈

N30:CH₄

NGlymc:62Au₂

imaging-Placentacellcomplextotal

ion

Namc:2555tc:19856487

mc:227sample:placenta

Pl:Au2Polarity:positivAlamc:89tc:547761Valmc:56tc:362584Sermc:42tc:214306Phemc:26

tc:141978Field

ofwiew.64.4×64.4μm=Tyrme:15

tc:69353Camc:14

tc:70567Lecithinmc:17

tc:60066amino

acidstc:3149260sum

ofmc:479F—10μmPromc:144mc:36tc:216759mc:64tc:362318tc:1739607tc:359347tc:874854corpuscallosumcaudateputammencanterioicommissurenucleustriangularis

septiMouseBrainSectionCorrelationAnalysis:3ColourOverlayExample

provided

by

Alain

Brunelle,ICSN,CNRS,Francesum

of

phospholipidionssum

of

cholesterolionsFie

ld

of

View:8x8

mm²FeFie

ld

of

View:18x

18

mm2Field

of

view:18000.0×18000.0μm²255283771892CarboxylateTriclycerideRat

BrainCrossSectionred=(255+283)green=892

blue=771to

be

published

byA.Brunelleet.al.ICSN,CNRS,FranceC18

Fattyacidred=283blue=255PhospholipidFieldofView:52.7x52.7

μm²one

pixel:100×100

nm2-

only

100shotsapplied

一

20integral

countsx10°6.0+5.0-4.03.02.0-Salbutamol(M+H)+maxcounts:20total

counts:2.12x105→2x10-20moledetectedfroma

100

nmspotSalbutamolSalbutamol210200220230240180190Applications

in

LifeSciences▶FundamentalresearchTissues,cells,membranes,biopolymers,lipids,

…

…Biomedicine,biology,biochemistry

…

…

…

…▶DiagnosticsBiochips,chromatographies,nanofluidics,marker,molecular

pathology,..

…▶DrugsDelivery

systems(tablets,nanoparticles,polymers,…),localisation▶BiomaterialsArtificial

membranes,substrates

for

cell

growth

and

artificialin

cells

and

tissues(ADME),contamination,screening,

…

…tissues,protein-and

cell-adhesion,biocompatibility,

…

…Directionsoffuturedevelopment▶FundamentalresearchUnderstandingthesecondaryionformationprocess▶Technicaldevelopment

ilvi

olution:

a

z