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c) Examples
EDX
Marco Cantoni
X-ray generation:
Inelastic scattering of electrons at atoms
Eelectron_in > Eelectron_out
SE
SE,
BSE,
EELS
EDX
Marco Cantoni
Forbidden transitions !
quantum mechanics:
conservation of angular momentum
EDX
Marco Cantoni
Light elements
Auger
Spectroscopy
Heavy
elements
EDS
SEM
Cu-K 8.1kV, HT
15kV
U = 15/8.1 = 1.85
TEM ->
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
Continuum,
Bremsstrahlun
g
10keV
EDX
Duane-Hunt limit
Marco Cantoni
8
c) Quantification
First approach:
compare X-ray intensity with a
standard (sample with known
concentration, same beam current of
the electron beam)
ci: wt concentration of element i
Ii: X-ray intensity of char. Line
ki: concentration ratio
EDX
Quantification
Yes,
but..
ci
I
stdi ki
std
ci
Ii
Marco Cantoni
When the
going gets
tough..
Correction matrix
ci
Ii
Z A F std std ki
ci
Ii
EDX
Marco Cantoni
10
Is the difference
between the new and the
old concentrations smaller
than the calculation
error?
no
EDX
Yes !
Marco Cantoni
stop
11
Correction methods:
ZAF (purely theoretical)
PROZA Phi-Rho-Z
PaP (Pouchou and Pichoir)
XPP (extended Puchou/Pichoir)
EDX
Marco Cantoni
12
EDS in TEM
Thin samples -> correction factors
weak (A and F can be
neglected)
Very weak beam broadening ->
high spatial resolution ~
beam diameter (~nm)
EDX
Marco Cantoni
13
Interaction volume
PZT
ceramics
bulk
Small interaction
volume -> high spatial
resolution for EDX
Analysis!
20nm
thick PZT
TEM
MSE-635 Spring 2013
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
Ternary systems
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
Mg
Si
Spectrum 1
Spectrum 2
Spectrum 3
Spectrum 4
Spectrum 5
Spectrum 6
Spectrum 7
Spectrum 8
Spectrum 9
30.02
19.15
6.01
5.65
5.63
5.98
5.55
5.49
5.63
13.32
7.96
Max.
Min.
30.02
5.49
13.32
7.96
Nb
Pb
Total
4.11
12.49
12.39
12.48
13.66
12.45
12.96
12.19
11.72
22.13
22.67
22.52
20.11
22.66
21.84
23.04
56.66
57.06
59.37
59.29
59.36
60.25
59.34
59.72
59.14
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
100.00
13.66
4.11
23.04
11.72
60.25
56.66
EDX
Marco Cantoni
EDX
Marco Cantoni
Marco Cantoni
EDX Line-scan
EDX
Marco Cantoni
Zr
Ti
Pb
Total
Zr/Ti
8.43
12.60
18.45
60.52
100.0
40/60
9.92
9.98
20.15
59.95
100.0
49/51
12.07
7.61
20.49
59.84
100.0
61/39
Spectrum
EDX
Marco Cantoni
EDX
Marco Cantoni
Artifacts
EDX
Marco Cantoni
0.5 mm
Marco Cantoni
Processing
bronze route
Ti
Cu,Sn
bronze
Ti
Nb3Sn
Heat treatment
Nb Ta
Nb
Cu,Sn
SEM: reacted filament (1 out of 14000)
MSE-635 Spring 2013
EDX
Marco Cantoni
Typical problems:
thinning of heterogeneous specimens:
selective thinning
bronze
Nb3Sn filament
EDX
Marco Cantoni
15um
SEM (FIB)
Ion milling
thickness:40-50nm
STEM-DF
FIB
Sample #21
MSE-635 Spring 2013
EDX
Marco Cantoni
Spot analysis
Line profile
Nb3Sn
bronze
Nb
Tc/Jc
useful
Point
Ti
%at
Nb
%at
Sn %at
Ta
%at
0.1
79.7
17.1
2.9
0.4
79.2
17.8
2.4
0.8
77.8
18.5
2.7
1.8
75.1
20.8
2.1
0.5
76.5
20.9
1.9
0.2
74.3
23.1
2.2
1.6
73.1
23.4
1.7
1.2
73.7
22.8
2.1
0.9
70.4
26.4
2.1
Sample #21
MSE-635 Spring 2013
EDX
Sn
Marco Cantoni
Nb
Ti
Ta
Sn
Sample #21
MSE-635 Spring 2013
EDX
Marco Cantoni
Cu
Nb
Ta
Ti
Quantitative Line-scan
Sample #24
Sn
EDX
Marco Cantoni
X-rays
SDD
Thickness
Area
Det. Interval
Speed:
Cooling
MSE-635 Spring 2013
EDX
SDD
Si(Li)
300-400m
3mm
2
30mm2
30,50,80mm
4-10sec.
50-100sec.
100000cps
10000cps
Peltier
Liq. N
Marco Cantoni
TECNAI OSIRIS
Analytical TEM
2012 @ CIME
5x
electrons
10x
Det. area
EDX
Marco Cantoni
Sn
Nb
Cu
STEM DF
EDX
Marco Cantoni
Sn
Cu
EDX
Marco Cantoni
EDX
Marco Cantoni
HAADF
STEM
La at grain
boundaries
Cl (from
synthesis)
MSE-635 Spring 2013
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
EDX
Marco Cantoni
BF and DF HAADF
images of window 1
Cr
STEM EDS mapping revealed the presence of Cr-S rich precipitates that might contain
also oxygen. However, oxygen was not taken into account since its proper quantification
at very low quantities is difficult.
MSE-635 Spring 2013
EDX
Marco Cantoni
EDX
Marco Cantoni
Precipitate 1- window 1
Element
series
[wt.%]
Chromium K-series
Copper K-series
Sulfur K-series
Sum:
2.85
95.50
1.65
100
[norm.
wt.%]
2.85
95.50
1.65
100
[norm.
at.%]
3.41
93.39
3.21
100
Precipitate 2 window 1
Error in
wt.%
0.15
2.08
0.11
Element
series
[wt.%]
Chromium K-series
Copper K-series
Sulfur K-series
Sum:
3.40
95.39
1.21
100
[norm.
wt.%]
3.40
95.39
1.21
100
[norm.
at.%]
4.08
93.58
2.34
100
Error in
wt.%
0.18
2.13
0.11
The precipitates contain chromium and sulfur and their ratio is close to 1:1. The peaks at
K (5.411) and K lines for chromium and K for sulfur are evident.
MSE-635 Spring 2013
EDX
Marco Cantoni
Element
series
[wt.%]
[norm.
[norm.
wt.%]
at.%]
0.0100 0.0123
99.9900 99.9877
0
0
100
100
Error in
wt.%
0.0003
2.0249
0
EDX
Marco Cantoni
EDX
Marco Cantoni
Outlook:
STEMEDXtomographyon
nanometricdevices
KevinLepinay1*,F.Lorut1,R.Pantel1,T.Epicier2
1STMicroelectronics,Crolles,France
2MATEISLab,INSALyon,France
kevin.lepinay@st.com
Microscopyneedsinsemiconductorindustry
Needsinchemicalanalysis materialscomposition,diffusionanddopants
EDXtechnique(photondetectionfromelectronionization)
EDXmappingsinonlyafewminutes, detectingmostofelementseven
dopants suchasArsenic.
EDXSTEM
TEM
Si
Ti
Hf
As
Ni
EDXmappingofa32nmNMOStransistor[R.Pantel]performedontheTecnai OSIRIS
Theideaisthecouplingofthesetwotechniquestoobtainananometric3D
chemicalanalysis.
STEMEDXtomographyprinciple
EDXmappingacquisitionateachtiltangle
TomographyspecificFIBsamplepreparationneedleshaped
Preparedsample needlediameter
between100nmand200nm(TEMimage)
Samplepreparationstrategy(SEMimages)
STEMEDXtomographyanalysisflow
ACQUISITION Esprit
Nickel
ManualStep:
Tilt rangedefined
Dose(probecurrent,EHT)
EDXDwelltime
EDXmapping
800x800px
5min/map,step
2
DATAEXTRACTION Esprit/ImageJ
Tungsten
Copper
ManualStep:
Tantalum
ExtractionofallelementalmappingfromeachEDXmapping
ImageJ treatment(8bitconversion,operations,filtering)
RECONSTRUCTION Inspect3D
SemiAutomatedStep:
Alignment
MRCvolumecreationforeveryelement
parameters
Alignmentshiftscalculationwith1element
Applyalignmentshiftstoeveryvolume
SIRTReconstruction
VISUALISATION Amira
ManualStep:
Volumerenderingcreation
Informationextraction(ex:defectmorphology)
Titanium
Experimentalmethodandcasestudy
Acquisitionparameter:
EHT120keV,probecurrent:1nA
Tiltrange180,tiltstep2
Dwelltime500s,mappingacquisition5min/map
Ni
W
Cu
Ti
3DchemicalrenderingofFDSOI
transistor
Voxelrepresentationcanbeobtained
Elementperelement
Combinationofelements
3Dchemicalrepresentationperelement
Ta
Ti
Si
Cu
Ni
Hf
Experimentalmethodandcasestudy
Extractedslices inalldirections
Paralleltothegatestack
Ni/Si/Ti/Hf
STIstepheight
Nomaskingeffect
Perpendiculartothegate
Ni/Si/Ti/Hf
CuMetalline
TaN Barrier
Ta
Ti
Si
Cu
Ni
Hf
Inplugs
Wplugs
TiN Barrier
NiSi siliciuration