© sas, icxom xviii 2005 pdf/x... · confocal μ-xrf Ìcrossed-beam voxel (≈15-20 μm)...
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© SAS, ICXOM XVIII
Alexandre SimionoviciLab. de Sciences de la Terre, ENS - Lyon
© SAS, ICXOM XVIII
Lab. de Sciences de la Terre, École Normale Supérieure - Lyon
L. LemellePh. Gillet
P. Soudant
ESRF, GrenobleP. Bleuet
Univ. of SassariB. Golosio
IMT,Russian Acad. of Sciences
M. ChukalinaLaszlo Vincze, Univ. of GhentCh. Rau, Univ. of ChicagoAntonio Brunetti, Univ. of Sassari
© SAS, ICXOM XVIII
Uncertainties for Kα et Lα
5 − 25 %
Fluorescence cross-sections σ
M.O. Krause et al., ORNL-5399
© SAS, ICXOM XVIII
Brunetti, Sanchez del Rio, Golosio, Simionovici, SomogyiSpect. Acta B 59, 1725-1731,(2004)
X-ray database: XRAYLIB
multi-OS/multi-languagefluorescence/absorptionCompton/Rayleigh (pol/non-pol)form-factor, scatt. functionTransition/Edge energies
Z=13
Z=80
http://www.esrf.fr
© SAS, ICXOM XVIII
Accurate quantification by Monte-CarloL. Vincze, Univ. of Ghent
250 µm thick Si-waferLive time: 1000 sInstrument: ID18FE0 = 27 keVEphotoelectron = 25.16 keV
K photoelectron bremsstrahlungL photoelectron bremsstrahlung
fluorescence
photoelectron impact ionization
Si
Ar
full simulation
experiment
Single + multiple Compton
Simulation without photoelectron tracing
Collaboration: J. Osan, Sz. Török,, KFKI, Budapest, Hungary
© SAS, ICXOM XVIII
I0 Abs. Det.
Totalfluo.
Thick target mapping - IFast
counterE dispersive det.Slow (>0.5 s/pt)
Fluodet.
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Fluodet.
Δx
Δy
Thick target mapping - II
loss of resolution ~ Δyaverage of concentrationsNO self-absorption corrections
Limited imaging
Qualitative
But FAST
© SAS, ICXOM XVIII
GEOMETRY problem
SELF-ABSORPTION problem
LOW Z (≤ 14) fluorescence
Problems in X-ray mapping
DETFocused
beam
penetration
multi-element
Z > 14
+ -
© SAS, ICXOM XVIII
e--beam mapping
“skin” mapping
Energy distribution
Range distributions
Quartz Steel
resolution ~ μmlocal concentrations > 1‰
E = 20 keV
© SAS, ICXOM XVIII
Spectroscopy- fluorescence- absorptionImaging- abs. tomographyDiffraction- WAXS/SAXS
Beamline for X-ray microanalysis & microscopyCOUPLED ANALYSES- Fluorescence + Diffraction- Tomography + Fluorescence
K-B
microscope
CCDCCDDiff
Si(Li)
detectorYZ Rθ
2 µm/step
Sample holder0.1 µm/step or
5 nm/stepXYZ Rθ Rφ θ
YZ1 µm/step
< ppm
≤ µm
Talk by Isabelle Letard, ESRF: 13 element Si(Li)
© SAS, ICXOM XVIII
Solution :fluorescence tomography
polar scan z et θlong acquisitionreconstruction : inverse pb.
Simionovici et al., IEEE Trans. Nucl. Sci., 47, 2736-2740 (2000)SPIE 3772, 304 (1999)SPIE 5535, 232 (2004)
© SAS, ICXOM XVIII
Problem: unmeasured fluorescences (Z<14)- self-absorption- matrix density
Solution:
I T T: Integrated Tomographic Techniques
SART (FT, Compton, transmission)
Optimal estimate functions ρ, μ
First fully quantitative reconstruction method
© SAS, ICXOM XVIII
Transmission tomographyART (Algebraic Reconstruction Technique)
f1 f2
fn+1
fn
f2n
fn×n
gi
j
gij+1
jth rayof width τ
Area of the intersectionijka
τ=
Image : square grid of n × n = K pixels
fk = absorption coefficient at the pixel k
Ray integrals : gij = g(θi , sj ) θi (i=1,…, Z) , sj (j=1,…,J)
∑=
≈K
kk
ijk
ij fag
1
)()(
τ
© SAS, ICXOM XVIII
ART (Algebraic Reconstruction Technique)
• System of I× J linear equations with the unknowns fk• Initial guess of the image fk (normally set to zero)• Estimate for the ray integral:
( )(
1
)K
ijk k
k
ij a fq
=
≈ ∑
• This must be compared to the measured ray integral gij
• The content of all pixels intersected by the ray is updated in order to obtain the correct value of the integral :
( ))
( )
((
1
) iji
k jk Ki
jk
ij
k
qa
a
gf
′′=
−Δ =
∑
• The difference between gij and qi
j is distributed among all pixels intersected by the ray in proportion to their weights
© SAS, ICXOM XVIII
Fluorescence Tomography Fluorescence signal on the detector at 90°• Only the points intersected by the beam contribute• Contribution of a small path du :
• εD is the efficiency of the detector• f(s,u) is the probability that a photon from the
source reaches the point U
• pα(s,u) is the probability of fluorescent emission by an atom of type α along the path du
• gα (s,u) is the probability that a photon emitted from U reaches the detector
( ) ( ) ( )duusguspusfI D ,,,0 ααε
( ) ⎟⎟⎠
⎞⎜⎜⎝
⎛′′−= ∫
∞−
udusEusfu
,,exp),( 0μ
( ) duNduusp ααα σ=,
( ) ⎟⎟⎠
⎞⎜⎜⎝
⎛−Ω= ∫∫
Ω
dllEdusgDet
usD ),(
,exp41),( αα μπ
( ) ( ) ( ) ( )∫+∞
∞−
= duusguspusfIsS D θθθεθ ααα ,,,,,,, 0Total signal measured by the detector :
Translation-rotation systemEnergy sensitive detector at 90°Counter/detector in the forward direction
Y
X
s translation
u
Fluorescencedetector
Sample
Beam
Transmissiondetector
rotationθΩDl
© SAS, ICXOM XVIII
Compton Tomography
• Analogous to fluorescence tomography, • Based on the signal due to Compton scattered photons
• Non-isotropic differential cross section
Momentum transfer :
• For q ≥ 20 keV, the binding of electrons to the atoms is neglected (free-electrons approximation) ⇒ σC ∝ Z
200
)cos1(1 cmEEEe
=−+
=′ αθα
⇒ provides a map of the electronic density spatial distribution
• For q < 20 keV, the atomic wavefunctions of the electrons must be considereσC ∝ S(q,Z) incoherent scattering function
• In the same conditions, Rayleigh scattering is also important: σR ∝ Z2
0 sin2
q E θ=
© SAS, ICXOM XVIII
Golosio, Simionovici et al,J. App. Phys. 94, 145-156, 2003
Compton/(Rayleigh/Transmission)μ′ and ρ optimal functions
0 0( ), ( , ) ( '),, 0; 2
, ; /min max
, ( )
ScatE p E Emeasurements
bounded
optimal rms
μ μ ρρ μ
ρ μ
ρ μ
Θ> ≥
∃
→
↓
↓
+
E0=25 keVΘ = 90°, φ =90°
6 ≥ Z ≥ 15
Global valuesfor Z elem.unavailable
ε ≈ 12 % ε ≈ 10 %
ε ≈ 5 %
μ′ μ′
ρ
© SAS, ICXOM XVIII
Projections: 180° for FBT, 360° for ART
FBT: no corrections for reflection geometry, no (self) absorptionfaster, adapted to homogenous samples but « artifact-prone »
ART: robust, easy to add corrections, better resolution
Reconstruction: ART versus FBTART
FBT
Fe Ni Cd Sr
resolutio
n = 5 µm
Simionovici et al, SPIE 3772, 304 , 1999
© SAS, ICXOM XVIII
Mycorrhizal root of tomato plantMycorrhizal root of tomato plantroot root -- Ø < 0.5 mm; resolutionØ < 0.5 mm; resolution ≈≈ 1 µm1 µm
K Ca Fe
Cu Zn Pb TransmissionSimionovici et al, Nucl. Instr.& Meth. A 467-468, 889-892, 2001
Schroer et al, SPIE 4503, 230-239, 2001
Environmental study of metal extraction from polluted soils
© SAS, ICXOM XVIII
Search for traces of life on micro-meteorites
Non destructive imaging of carbonatesites of formation of bacteriomorphsComplementary to IR, SEM/TEM studiesPreparation for MARS RETURN- mini-container (BSL 4)
Simionovici et al,SPIE 4503, 222-229, 2001
Golosio et al., Jrnl. App. Phys. 94, 145-157, 2003
Lemelle et al, Am.Mineral. 87,547-553, 2004
Simionovici, Schroer, LengelerAdvances in X-Ray Spectrometry,John Wiley & Sons, 2004
-30
-20
-10
0
10
-30 -20 -10 0 10
Fe
CaSi Cr
Fe
Si2 μ resolution
2 sec/pt
-30
-20
-10
0
10
-30 -20 -10 0 10
Tatahouine
Distance (μm) Distance (μm)
© SAS, ICXOM XVIII
Reference sample :6 thin metal wires in a quartz capillary
Quartz capillary• 100 μm diameter at the bottom• 10 μm wall thickness
Quartz capillaryGlue2 Aluminum wires d = 20 μm1 Copper wire d = 20 μm2 Nickel wires d = 25 μm1 Tungsten wire d = 10 μm
Sample geometry and composition
© SAS, ICXOM XVIII
Metal wires inside a capillary:Transmission and Compton tomography
• Translation : 160 steps of 3 μm each• Rotation : 180 angular steps of 2° each
Transmission tomography Compton tomography
Transmission tomography• Only the higher Z metal wires are clearly distinguishable in the image
( Absorption cross section ~ Z4 )
Compton tomography• The lower Z objects (Al wires, glue, capillary) are clearly distinguishable
( Compton cross section ~ Z )
© SAS, ICXOM XVIII
Combined experiments:FT - AT
tomo (1 μm) fluo-tomo (2 μm)
Ca/Fe ratio
A
B
A B
Radiography
Martian meteoriteNWA 817
© SAS, ICXOM XVIII
Fluorescence tomography reconstructions
Iron Manganese
• Fe density 1.45 g/cm3
• Mn density 0.058 g/cm3
• Total density 3.89 g/cm3
• Fe weight fraction 37.2%• Mn weight fraction 1.50%
Compatible with EPMA analysis
Golosio, Simionovici et al,J. App. Phys. 94, 145-156, 2003
Transmission ~ Z4
Compton~ Z
Rayleigh~ Z2
Results
© SAS, ICXOM XVIII
diatom: voxel: 2x2x2 µm3 , Vol: 100x 100 x 80 µm3
FI (full scan) interpolation, 12 µm pitch, 120 rot.dose/ time, same or better resolutionvolume segmentation, visualization, renderingvolume processing: extraction, measurement
density Br
Golosio, Somogyi, Simionovici, Bleuet, Lemelle,App. Phys. Lett, 84, 2199-2201, 2004
3D elemental imaging byspiral fluorescence tomography
200 μm
© SAS, ICXOM XVIII
Compton CdCa Fe
Camerani Pinzani et al., Anal. Chem. 76, 1586-1595, 2004
Flyash chemistry:C. Camerani et al. , Chalmers Univ., Gøteborg
Density
Mn ––––
Rb ––––
Fe ––––
© SAS, ICXOM XVIII
Origin of primitive meteorites:chondrites (Semarkona/Krymka)
oxydized chondrules(FeO, FeS)
reduced chondrules(metals)
Study of processes during chondrule formation:evaporation + chemical fractionation
(trace anal. Cu, Zn)
© SAS, ICXOM XVIII
10-3 g/cm3g/cm3
Fe Ti Cr
Transmission
cm-1
μ
10-3 g/cm3
Mn Cu ZnNi
10-3 g/cm3 10-3 g/cm3 10-3 g/cm3 10-3 g/cm3
Combined FT&AT- Localization of chondrules/CAI by AT ≈ 1 µm- Direct elemental imaging
250 μm : 1 x 2 μm2
FTslice
250 µm
© SAS, ICXOM XVIII
Environmental markers: foraminifera
Transmission
Ca Ni
100μm
100μm
Ca Cu
100μm100μm
Ca Zn
Ca
100μm
© SAS, ICXOM XVIII
Time savings in FT
Regular scan Sine-fit scan- 30 %
Smart scan- 50 %
Smart scan: - robust, alignment-less- threshold: Compton⊗Fluo- pad to fix matrix- great time gains >50%
Zap scan: - continuous scan for transl.- NO overhead- limited dwell range 0.1-1 s- split line into MCA spectra- abs. time gains >0.5 s/point
1.5th generation : 2 sym. detectors- tricky alignment 1st time- 1/2 time
© SAS, ICXOM XVIII
Confocal μ-XRF
crossed-beam voxel (≈ 15-20 μm)semi-quantitative reconstructiondepth profiling/ layering
possibility of XAS measurements
only way for single-side access
possibility of local tomography
straighforward XYZ scanning
lower scattering volume
© SAS, ICXOM XVIII
B. Kanngiesser, W. Malzer, I. ReicheNucl. Inst. & Meth. B 211, (2003) 259–264B. Kanngiesser, W. Malzer, A. Fuentes Rodriguez, I. ReicheSpectrochimica Acta Part B 60 (2005) 41– 47
Confocal μ-XRF I
μ-layering of paint: Hg, Pb (10 μm)
Dating of a Mughal miniature – 18th century3 layers of paint: Pb, Pb+Zn+Sn, Pb
© SAS, ICXOM XVIII
Z. Smit, K. Janssens, K. Proost, I. Langus, NIM B 552, 219–220 (2004) 35– 40.
K. Janssens, K. Proost, G. Falkenberg,Spect. Acta B 59, 533 (2004) 1637– 1645.
Confocal μ-XRF II
Fe and Sr maps at various depthsGranite 100 μm thin slideResolution : 15 - 30 μmMDL 0.1 ppm, < 1 fg for Fe-Zr
© SAS, ICXOM XVIII
L. Vincze, B. Vekemans, F.E. Brenker, G. Falkenberg, K. Rickers, A. Somogyi, M. Kersten, F. Adams, Anal. Chem. 76 (2004) 6786– 6791.
B. Vekemans, L. Vincze, F. Brenker, F. Adams, JAAS 19 (2004) 1302– 1308.
Confocal μ-XRF III
Inclusions (Zr, Sr, Th) in mm-sized diamondsMDL ≈ 50 ppm (Zr)Resolution 15-30 μm (Zr, Ca)
© SAS, ICXOM XVIII
XCFT C-XRF
DET
Dose deposition
det
© SAS, ICXOM XVIII
Quantification requirementsaccuracy of tabulated values (σ, μ)
normalization, stability: position, angle, flux = f (t)
sample heterogeneity/geometry corrections
enhancement (2nd, 3rd)
photo-ionization from scattering (C, MS)
photo-ionization from photo-e- bremsstrahlung
electron impact ionization by Auger & photo-e-
linear polarization correction for incident flux
detector response (tails, internal Compton, efficiency)
energy dependence of the excitation (ΔE≠0)
angular distribution of signal (detection angle)
spectral purity (higher orders contribution)
© SAS, ICXOM XVIII
EXRS 2006European Conference on X-Ray Spectrometry
June 19-23, 2006 - PARIS, France
Chairs: Marie-Christine LEPY, CEA SaclayAlexandre SIMIONOVICI, ENS Lyon
http://www.nucleide.org/exrs2006
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