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