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Henri-Noël Migeon
Département “Science et Analyse des Matériaux”
CRP-Gabriel Lippmann
41, rue du Brill
L-4422 Belvaux
La Spectrométrie de Masse d'Ions Secondaires
(SIMS):
un outil majeur pour l'étude de notre système
solaire, les recherches biomédicales et le
développement des nanomatériaux
The nanometer scale
100 microns
Luxembourg/Nancy: 117 km
100 microns / 100 km = 10-9
1nm / 1 m= 10-9
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
Secondary lon MassSpectrometry (SIMS) is basedupon the sputtering of a fewatomic layers from the surface of asample induced by a “primaryion” bombardment. A primary ionimpact triggers a cascade ofatomic collisions. Atoms, moleculefragments and ions are ejected
C60 bombardment - animation
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
Sensitivity
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
Primary
ionsEjected
particles
Chemical analysis
(elemental and isotopic)
Target
Mass spectrometerSeparation by mass to charge ratio
(m/z)
Secondary ions emission
Neutrals (majority)
Charged particles
electrons
Secondary ions
positive ions
negative ions
Radiations
Secondary Ion Mass Spectrometry
Georges Slodzian
Université Paris-Sud Orsay
Raimond Castaing
(1921 – 1998)
André Guinier est né à Nancy où son père Philibert Guinier,membre de l’Académie des Sciences dans la section d’économierurale, était directeur de l’École Forestière. Il entre à l’ÉcoleNormale Supérieure en 1930 et prépare une thèse encristallographie. Ses premiers travaux sont consacrés à laconception et à la réalisation d’une chambre de diffraction desrayons X qui permet d'étudier la diffusion des rayons X auvoisinage immédiat du faisceau incident.C'est en étudiant les défauts cristallins que Guinier découvre (enmême temps que Preston) ce que l'on a appelé les “zones deGuinier-Preston”, zones de concentration de l’un des typesd’atomes composant un alliage (le premier exemple fut Al-Cu). Ces“zones G-P” ont un grand intérêt en métallurgie.Après sa thèsesoutenue en 1939, il propose le sujet de thèse de Raimond Castaingqui donnera lieu à la Microsonde de Castaing.
Alfred Benninghoven
Université de Münster
Static SIMS
Dynamic SIMS
Electron microprobe
Direct image ion microscope
Georges Slodzian, Thèse (1964))
Si+ Mg+
Al+
Radius # B-1 (m/q)
Claude Allègre,prix Crawford (= prix Nobel de Géologie)
membre
correspondant
Georges Slodzian
IMS 1280
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
1,00E+01
1,00E+02
1,00E+03
1,00E+04
1,00E+05
1,00E+06
1,00E+07
1,00E+08
1,00E+09
20 22 24 26 28 30
Masse (amu)
cnt
23Na+
24Mg+ 28Si+
29Si+ 30Si+25Mg+
Mass Spectrometry
26Mg+
100 200 300 400 500 600
0
5000
10000
15000
Ab
on
da
nce
(i.a
.)
m / z
Fingerprint of the polymer
Detection of elements
Detection of additives :- Poly(ethyleneglycol)dibenzoate
- Poly(ethyleneglycol)monobenzoate
Mass Spectrometry
Mass Spectrometry
Ion imaging
Masse 3
1
Masse 1
2Ma
sse 2
6
Masse 127
Ions
secondaires
12C- 12C14N- 31P- 127I-
Echantillon
Ions
primaires
2 m
NanoSIMS 50 :MulticollectionMulticollection
Ion imaging
Carbure detungstène
1E+04
1E+05
1E+06
0 2 4 6 8
μmIn
tensit
é C
(coups)
12C
Vérification de l’homogénéité du liantDiffusion dans le liant
12C
12C14N
12C
2,3μm
0,78μm
Ion imaging
Depth profiling
- roughening effectroughening effectss (non-flat bottom crater)
High depth resolution requires
low impact energylow impact energy (250eV to
1keV) and convenientconvenient primary
beam incidence angleincidence angle
The depth resolution is limited by:
- - collision cascades collision cascades (target atoms mixing)
- crater edge effect- crater edge effectss (crater walls)
Depth profiling
CAMECA IMS6f GVB sans rotation
1,E-01
1,E+00
1,E+01
1,E+02
1,E+03
1,E+04
1,E+05
1,E+06
1,E+07
1,E+08
1,E+09
0 10 20 30 40 50 60 70 80Profondeur en nm
Inte
nsit
é e
n c
/s
133Cs
133Cs48Ti
133Cs64Zn
133Cs107A
g 133Cs2
Depth profiling
3D analysis
Carbon in a Thin-Film Superconductor RAE (IMS 3f)Carbon in a Thin-Film Superconductor RAE (IMS 3f)
3) Imaging + sputtering= 3D
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
Trace element mapping
GOLD ANALYSIS IN ARSENOPYRITE
Au- ion image
Field of view 100 x 100 m2
Arsenopyrite: FeAsS
4) Isotopic ratio measurements
Geochronology
3.896
3.900
3.904
0 2 4 6 8 10
Spot #
11B
/10B
Counting statistics error : 0.08 per mil
Experimental error (1 ) : 0.08 per mil
error bar : +/-1
-10.0
0.0
10.0
20.0
0 5 10 15 20 25 30
Spot #
Delt
a 1
8O
(p
er
mil)
kim5-grain#1
mog_grain#1
kim5-grain#2
kim5-grain#3
Counting statistics error : 0.12 per mil
Experimental error (1s) : 0.17 per mil
25
27
29
31
0 1 2 3 4 5 6 7 8 9 10 11
Spot #
Delt
a 3
0S
i (p
er
mil)
Counting statistics error : 0.40 per milExperimental error (1 ) : 0.45 per mil
Error bar : +/-1
SILICON ISOTOPES IN GLASS BORON ISOTOPES IN TOURMALINE
OXYGEN ISOTOPES IN ZIRCON
Geochronology
Geochronology: Zircon radiodating
Zircon is one of the most useful
geochronometers.
Courtesy of NORSIMS
Zircon: ZrSiO4
remarquably resistant material
two clocks:
235U 235U 207Pb 207Pb (( ~ 0.7 billion ~ 0.7 billion yearsyears))
238U 238U 206Pb 206Pb (( ~ 4.4 billion ~ 4.4 billion yearsyears))
Oldest zircon: ~4.40 billion years (Australia)
Age of the Earth: ~4.55 billion years
O2- primary ions , w/o
oxygen flooding
Geochronology
sample
primary beam
secondary beam
O2 jet
O2- primary ions , with
oxygen flooding
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
Radiotoxicology
/ Nuclear medecine:
Imaging 127I/ 129I
distribution in thyroid
Raster 60x60 m2
1212CC1414NN 3131PP
129129II127127II
J. L. Guerquin-Kern , Curie Institute, Paris
Bio Med
Field of view:10 m x 10 m
Incorporation of BrdU (bromodeoxyuridine), IdU (iododeoxyuridine) and5FU (5-fluorouracile) compounds in the same cell.
The last four images are collected simultaneously from same sputtered volume (multi-collection).
Sample from Pr. P. Galle, S.C. 27 INSERM, Faculté de Médecine, Créteil, France
32S
31P
127I
12C
14N
-
81Br
19F
MCF-7 mammary carcinoma cell:use of halogenous markers
Bio Med
Bio Med
12C14N
31P31P
127I
0.5 m
NanoSIMS
Pharmaco-toxicology:Targeting melanin cells
• CN :proteins
• P :DNA
morphology
I
General Structure of BZA
J. L. Guerquin-Kern , Curie Institute, Paris
Bio Med
E.coli labelled with 15N
at time t = t1
Natural abundance14N 99,7%15N 0,3%
E.coli labelled with 15N
at time t = t2 > t1
Bacteria destroyed by immune
system
12C14N 12C15N
Analyzed area : (12 x 12) μm2
12C14N 12C15N
Bacteria
Incorporation of an isotopically (D) labelled
active molecule in human hair
Analyzed area : (80 x 80) m2
1H 2H
Molecule CxDy
Biology, Cosmetic
Courtesy of L’Oreal
Bio Med
Hairs from St Hélène …….
Reference Hair Hairs from St Hélène
14N 15N
15N / 14N
(20x20) μm2
1,6μm
M.Challot, INRA, Nancy.
Identification of specific sites for N fixationHigh levels 15N
Mushroom cells cultured in 15N enrichedmedia, 15 min
15N: stable isotope tracer used in vegetal cells
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysi
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
Nanomaterials
R&D in Semi conductors
Image Image depthdepth profile in N-MOS profile in N-MOS gategate::
Oxygen Silicium Phosphorous Boron Arsenic
Depth = 0 nm
Depth = 300 nm
Depth = 650 nm
3) Imaging + sputtering= 3D
Nanomaterials
1. Ion/matter interaction : impinging andoutgoing particles
2. Instrumentation
3. General capabilitiesElemental range
Ion imaging
Depth profiling
3D analysis
4. ApplicationsGeochronologyBiomedNanomaterials
5. Future developments
Outline
High resolution NanoSIMS 50 images of 12C14N and13C15N of double-labelled Bacillus subtilis DNA combed on
wafers without Cs deposition (top) and with prior Cs
deposition (bottom).
Field of view : (15x15) μm2
Centre de Recherche Public – Gabriel LippmannBelvaux, LUXEMBOURG
4 departments: EVA / IST / SAM / REA
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