Lyman 6 - Spectrum Image (Fri)

PASI - Electron Microscopy - Chile
1
Lyman - Spectrum Imaging
Spectrum Imaging
Charles Lyman
Lehigh University,
Bethlehem, PA
Based on presentations by John Hunt (Gatan, Inc.), John Titchmarsh
(Oxford University), and Masashi Watanabe (Lehigh University)
2
Spectrum Imaging (SI)
Collect entire spectrum at each pixel
No a priori of specimen knowledge required
Can detect small amounts of elements in local
regions of x-y images
Away from microscope:
Repeatedly apply sophisticated spectrum
processing
Mine the data cube for features

Concept
Jeanguillaume & Colliex, Ultramicroscopy 28
(1989), 252
Demonstration
Hunt & Williams, Ultramicroscopy 38 (1991), 47

x
E
Scan
y
Incident
electron
probe
x-y-energy data cube
3
Elemental Maps from Data Cube
Data courtesy of David Rohde
Specimen: polished granite
0
200
400
600
800
1000
1200
1400
1600
1800
2000
x
y
Elemental
X-ray map
4
Quantitative Phase Analysis
Sum spectra for pixels within box
Enough counts for quatitative analysis
Data courtesy of David Rohde
Specimen: polished granite
5
Compositional Maps in TEM/STEM
Collection by:
STEM X-ray
Sequentially acquire EDS x-ray spectrum at each pixel (original concept)
Each x-ray entering detector assigned x-y-energy tag (Mott & Friel, 1999)

STEM EELS
Sequentially acquire EELS spectrum at each pixel

EFTEM (Energy-filtered imaging)
Sequentially acquire images at specific energies
One energy window for each energy channel in spectrum (DE)

6
A few Words about EFTEM
Elemental Maps
without
Employing Spectrum Imaging
7
EFTEM: In-Column and Post-Column Energy Filters
Omega Filter
Gatan Imaging Filter (GIF)
From Williams and Carter, Transmission Electron Microscopy, Springer, 1996
8
RGB composite Oxygen
Nitrogen
Carbon
Elemental Maps of a SiC/Si
3
N
4
ceramic

Short Acquisition Time (3 maps, 250K pixels) = 50s
Energy-Filtered TEM (EFTEM)
Element Maps - Not Spectrum Images
Courtesy John Hunt, Gatan
9
Energy-Filtering TEM
Images of only a small range of energies
Energy window of 1-100eV
Just above or just below energy-loss edge

EFTEM compositional mapping
Elemental maps using multiple energy-filtered images
2 images to determine background before edge
Scale background and subtract to obtain elemental signal
1 image to collect elemental signal (edge above background)

Only one electron energy can be precisely in focus
All other energies will be suffer resolution loss (blurring)

The blurr is given by:
d = C
c
*b

*DE/E
C
c
= chromatic aberration constant
b = the acceptance angle of the objective aperture
DE = range of energies contributing to the image
Blurr will be especially large for thick, high-Z specimens.
Reduce blurr by:
Using a small energy window (DE)
Select energy loss DE by changing the gun voltage (vary kV)

10
EFTEM Elemental Mapping
Three-Window Method
Subtract edge background
using two pre-edge
images (dotted line)
Element concentration
proportional to area of
edge above background
(outlined in red)
Absolute concentration
can be determined if
thickness and elemental
cross-sections are known
11
O Al Ti
Aluminum

Superimpose three color layers
to form RGB composite
Titanium
Oxygen
6 layer metallization test structure

3 images each around:

O K edge: @ 532 eV
Ti L
23
edge: @ 455 eV
Al K edge: @ 1560 eV

EFTEM Elemental Mapping: Example 1
1 m
12
EFTEM Elemental Mapping: Example 2
O
N
Si
Ti
Al
BF image
Unfiltered bright-field TEM image of semiconductor device structure and
elemental maps from ionization-edge signals of N-K, Ti-L, O-K, Al-K, and
Si-K.
Color composite of all 5 elemental maps
displayed on the left,showing the device
construction.
13
EFTEM detection limits
Typically 2-5% local atomic concentration of most elements
1% is attainable for many elements in ideal samples
10% for difficult specimens that are thick or of rapidly varying thickness

Sensitivity limited by:
Diffraction contrast
Small number of background windows
Signal-to-noise
Thickness
Artifacts

If you can see the edge in the spectrum, you can probably map it

EFTEM spectrum image can map lower concentrations than the
3-window method
Better background fits because there are more fitting channels
14
STEM & EFTEM
EELS Spectrum Imaging
15
STEM spectrum image acquisition
STEM spectrum image
acquired by stepping a focused
electron probe from one pixel to
the next

EDX
STEM
EELS
DF
Specimen
The spectrum image data
cube is filled one spectrum
column at a time
In STEM it is possible to collect
x-ray, EELS, BF, and ADF
simultaneously
Use of the ADF or SE signal
during acquisition permits
spatial drift correction
Dx
Dy
DE
16
Dy
Dx
DE
image at DE
1
image at DE
2
image at DE
i
.
.
.
.
.
.
.
.
.
EFTEM spectrum image acquisition
EFTEM spectrum image
Acquire an image containing
a narrow range of energies

The spectrum image data
cube is filled one energy
plane at a time

Image plane retains full
spatial resolution of TEM
image

17
STEM EELS spectrum imaging
EELS STEM SI acq. at 200keV (cold FEG)
xy: 50*29 pixels
E: 1024 channels (75eV, D=0.5eV)
Acquisition time: ~ 5 minutes
Processing time: ~ 5 minutes
18
Quantitative EFTEM Spectrum Imaging
EFTEM Spectrum Image
2.9 nm resolution
Si-L
23
: 75-150eV
{3eV steps} (1.5 min)
N-K, Ti-L, O-K : 350-650eV
{5eV steps} (8 min)
FEI CM120 + BioFilter
120keV
Corrections: x-rays, MTF, spatial drift
Scaled by hydrogenic x-sections

19
STEM vs. EFTEM Spectrum Imaging
Quantitative elemental mapping
Both STEM SI and EFTEM SI can do this

EELS STEM Spectrum Imaging
Good quality spectra
All artifacts / instabilities correctable
Usually safer w/unknowns

EFTEM Spectrum Imaging
Fast mapping
Uncorrected artifacts / instabilities are very dangerous
Very useful for well characterized systems
Excellent spatial resolution

20
X-ray Spectrum Imaging
21
Mining the SI Data Cube
Masashi Watanabe
Lehigh University

Nb(wt%)
1.5
0
Nb(wt%)
1.5
0
Multivariate Statistical Analysis of
X-ray Spectrum Images
22
X-ray Spectrum Imaging
Collection of SI
Huge data set
e.g. 256x256 = 65,536 spectra
each spectrum 1024 channels
cannot analyze manually
Noisier spectrum
for XEDS than EELS
Many possible variables
composition, thickness, multiple phases

100 nm
NiKa
TiKa
AlKa CrKa
FeKa
What can we do?
Specimen: Ni-based superalloy
Courtesy M. Watanabe
23
Multivariate Statistical Analysis
Problems for which MSA may be useful
1. Investigation of data of great complexity
2. Handling large quantities of data
3. Simplifying data and reducing noise
4. Identifying specific features (components) can be interpreted
in useful ways
E.R. Malinowski, Factor Analysis in Chemistry, 3rd ed. (2002)
Multivariate statistical analysis (MSA) is a group of processing
techniques to:
(1) identify specific features from large data sets (such as a
series of XEDS and EELS spectra, i.e. spectrum images) and
(2) reduce random noise components efficiently in a statistical
manner.
24
Nb map in Ni-base superalloy

Nb(at%)
1
0
Nb(at%)
1
0
100 nm
original
MSA-processed
Multivariate Statistical Analysis
identify specific features in the spectrum image
reduce random noise
25
The Data Cloud
Find greatest variancein
data
x1, x2, x3 are first three
channels of spectrum or
image
Manipulate matrices
Principal component
analysis finds new axes for
data cloud that correspond
to the largest changes in
the data
These few components
can represent data
26
Principal Component Analysis (PCA)
PCA is one of the basic MSA approaches and can
extract the smallest number of specific features
to describe the original data sets.
The key idea of PCA is to approximate the original
huge data matrix D by a product of two small
matrices T and P
T
by eigenanalysis or singular value
decomposition (SVD)
D = T * P
T
D: original data matrix (nX x nY x nE)
T: score matrix (related to magnitude)
P
T
: loading matrix (related to spectra)
27
Practical Operation of PCA
nX
nY
nE
spectrum image
PCA
D
nE
nX x nY
=
T
P
T
*
nX x nY
nE
D = T * P
T
D: original data matrix (nX x nY x nE)
T: score matrix (related to magnitude)
P
T
: loading matrix (related to spectra)
line profile
nE
nX
original data
score
loading
eigenanalysis
or SVD
eigenvalues
28
Spectrum Image of Ni-Base Superalloy
100 nm spectrum image:
256x256x1024
dwell time: 50 ms
20 eV/channel
matrix
g
M
23
C
6
NiKa
CrKa
FeKa
NiKa
CrKa
TiKa
AlKa
NbLa
Reconstructed spectra
29
Results of PCA 1
0 10 20
10
2
10
1
10
0
Component
E
i
g
e
n
v
a
l
u
e
STEM-ADF
200 nm
Loading
Score
scree plot
#1: average
#2: M
23
C
6
#3: g
Ti Ka
Al Ka
Ni Ka
Fe Ka
Cr Ka
Cr Ka
Ni Ka
Cr Ka
Ni Ka
Noise
30
Results of PCA 2
0 10 20
10
2
10
1
10
0
Component
E
i
g
e
n
v
a
l
u
e
STEM-ADF
200 nm
Loading Score
scree plot
#4: absorption
#5: noise

#6: noise
Ni Ka
Ni La
Cr Ka
Noise
31
Comparison of Maps
Al
wt%
2
0
wt%
2
0
wt%
1.5
0
wt%
1.5
0
Nb
100 nm
Compositional fluctuations below 2 wt%
can be revealed
Reconstructed
Original
32
Application to Fine Precipitates
Irradiation-induced hardening in low-alloy steel
is caused by fine-scale precipitation
Average precipitate size: 2-5 nm
X-ray mapping in VG HB 603 300 keV STEM
100 nm
BF-STEM image
ADF-STEM image
Burke et al. J. Mater. Sci. (in press)
33
Application to Fine Precipitates in Steel

(wt%)
Thickness
10 20
(nm)
STEM ADF Fe Cr
Ni Mn Cu
50nm
85 95 5
0 8 2 3 0 0.5
1
(wt%) (wt%) (wt%)
(wt%)
(wt%)
Mo
0
1
Too noisy
34
Application of MSA to Fine Precipitates
(wt%)
Thickness
10 20
(nm)
STEM ADF Fe Cr
Ni Mn Cu
50nm 85 95 5
0 8
1
(wt%)
(wt%)
(wt%)
Mo
0
1
1.5 3
(wt%)
0 0.8
(wt%)
35
Some References to MSA Procedures
Multivariate statistical analysis in general
S.J. Gould: The Mismeasure of Man, Norton, New York, NY, (1996).
E.R. Malinowski: Factor Analysis in Chemistry, 3ed ed., Wiley, New York,
NY, (2002).
P. Geladi & H. Grahn: Multivariate Image Analysis, Wiley, West Sussex,
UK, (1996).

For microscopy applications
P. Trebbia & N. Bonnet: Ultramicroscopy 34 (1990) 165.
J.M. Titchmarsh & S. Dumbill: J. Microscopy 184 (1996) 195.
J.M. Titchmarsh: Ultramicroscopy 78 (1999) 241.
N. Bonnet, N. Brun & C. Colliex: Ultramicroscopy 77 (1999) 97.
P.G. Kotula, M.R. Keenan & J.R. Michael: M&M 9 (2003) 1.

M.G. Burke, M. Watanabe, D.B. Williams & J.M. Hyde: J. Mater. Sci. (in press).
M. Bosman, M. Watanabe, D.T.L. Alexander, and V.J. Keast: Ultramicroscopy
(in press)
36
Summary
Spectrum Imaging
the way serious microanalysis should be done

Mining the data cube
MSA is applicable for large data sets such as line
profiles and spectrum images
The large data sets can be described with a few
features by applying MSA
PCA is useful for noise reduction of data sets.
Be aware -- MSA can provide only hints of significant
features in the data sets (abstract components)

Lyman 6 - Spectrum Image (Fri)

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

Lyman 6 - Spectrum Image (Fri)

Uploaded by

Copyright:

Available Formats

PASI - Electron Microscopy - Chile

You might also like