Energy-Dispersive

X-ray
Spectrometry
Charles Lyman
in the AEM
Based on presentations developed for Lehigh University
semester courses and for the Lehigh Microscopy School

PASI - Electron Microscopy - Lyman - EDS Qual 1

 Why Do EDS X-ray Analysis in
TEM/STEM?

● Spatial resolution
» 2-20 nm (103 times better than SEM/EPMA)

● Elemental detectability
» 0.1 wt% - 1 wt%, depending on the specimen (~same as SEM/EDS)

● Can use typical TEM specimens (t ~ 50-500 nm)

» EELS requires specimens < 20-30 nm

● Straightforward microanalysis
» Qualitative analysis => Which element is present?
» Quantitative analysis => How much of the element is present?
» Easy x-ray mapping

PASI - Electron Microscopy - Lyman - EDS Qual 2

 Example of an X-ray Spectrum

2 Types of X-rays

» Characteristic x-rays
– elemental identification
– quantitative analysis

» Continuum x-rays
– background radiation
– must be subtracted for quantitative
analysis

Example of EDS x-ray spectrum

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 3
 Continuum X-rays
● Interactions of beam electrons with nuclei of
specimen atoms

● Accelerating electric charge emits

electromagnetic radiation
» Here the acceleration is a change in direction

● The good
» The shape of the continuum is a valuable
check on correct operation
● The not-so-good
» I bkg increases as ib increases
» I bkg is proportional to Zmean of specimen
» I maxbkg rises as beam energy rises

● Peak-to-background ratio
Continuum
» Ratio of Ichar / Ibkg sets limit on elemental detectability x-rays

Absorption of
continuum

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 4
 Generation of Characteristic
X-rays
● Mechanism
» Fast beam electron has enough energy to
excite all atoms in periodic table
» Ionization of electron from the K-, L-, or M-
shell
» X-ray is a product of de-excitation

● Example
» Vacancy in K-shell
» Vacancy filled from L-shell
» Emission of a Kα x-ray (or
a KLL Auger electron)

● Important uses
» Qualitative use x-ray energy to identify
elements
» Quantitative use integrated peak intensity
to determine amounts of elements

PASI - Electron Microscopy - Lyman - EDS Qual 5

 Compute Energy of Sodium Kα Line

Beam
electron
If beam E > EK, then a
K-electron may be ionized: β
X-ray energy is the difference between α
two energy levels:
E Ka 1 = E K - E L III K L M
Energy levels EK and EL3 are in Bearden's "Tables
of X-ray Wavelengths and X-ray Atomic Energy
Levels" in older editions of the CRC Handbook of
Chemistry and Physics

For sodium (Z=11): EK = 1072 eV

Beam
EL3 = 31 eV electron
E Na
K a1 = 1072 eV - 31 eV = 1041 eV
loses EK

For Na only see one peak since the Kβ is only 26 eV from the Kα line
PASI - Electron Microscopy - Lyman - EDS Qual 6
 Families of Lines
If K-series excited, will
also have L-series

Note: this is a simplified version of Goldstein Figure 6.9 showing only lines seen in EDS
PASI - Electron Microscopy - Lyman - EDS Qual 7
 Fluorescence Yield ω
ω = fraction of ionization events producing characteristic x-rays
• the rest produce Auger e–
·
● ω increases with Z
» ω K typical values are:
– 0.03 for carbon (12) K-series @ 0.3 keV
– 0.54 for germanium (32) K-series @ 9.9 keV
– 0.96 for gold (79) K-series @ 67 keV
» X-ray production is inefficient for low Z lines (e.g., O, N, C) since mostly Augers
produced

● ω for each shell: ω K, ω L, ω M

» X-ray production is inefficient for L-shell and M-shell ionizations since

» ω Land ω M always < 0.5:
ω L = 0.36 for Au (79)
ω M = 0.002 for Au (79)

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 8
 X-ray Absorption and
Fluorescence
● X-rays can be absorbed in the specimen and in parts of the
detector æ ö m
- ç ÷r t
èr ø
I = I oe
Greater absorption when
-- x-ray energy is just above absorber absorption edge
-- path length t is large

● Certain x-rays fluoresce x-rays of other elements

» X-rays of element A can excite x-rays from element B
» Energy of A photon must be close to but above absorption edge energy
of element B
» Example: Fe Kα (6.40 keV) can fluoresce the Cr K-series (absorption
edge at 5.99 keV)

PASI - Electron Microscopy - Lyman - EDS Qual 9

 EDS Dewar, FET, Crystal

● LN dewar is most
recognizable part
» To cool FET and crystal

● Actual detector is at end

of the tube
» Separated from
microscope by x-ray
window

● Crystal and FET fitted as

close to specimen as
possible
» Limited by geometry inside
specimen chamber

Schematic courtesy of Oxford Instruments

PASI - Electron Microscopy - Lyman - EDS Qual 10

 Electron-Hole Pair Creation

Absorption of x-ray energy excites

electrons
» From filled valence band or states
within energy gap Conduction
band
Excited e-
Energy to create an electron-hole pair
» ε = 3.86 eV @ 77K Donor
(value is temperature dependent)
Energy
gap

y gr en E
Within the intrinsic region
» Li compensates for impurity holes Acceptor
» Ideally # electrons = # holes
» # electron-hole pairs is proportional Hole
to energy of detected x-ray Valence band

For Cu Kα :
8048 eV/3.8 eV = 2118 e-h pairs
(after drawing by J. H. Scott)

PASI - Electron Microscopy - Lyman - EDS Qual 11

 Details of Si(Li) Crystal

Anti-reflective Ice?
Al coating 30 nm Gold electrode
Gold
Silicon inactive layer (p-type) ~100 nm electrode
20 nm

X-ray

Holes Electrons

(–) (+)
Window
Be, BN, Active silicon
diamond,
polymer (intrinsic)
0.1 µ m — 7 µ m 3 mm
(after drawing by J. H. Scott)
–1000 V bias
PASI - Electron Microscopy - Lyman - EDS Qual 12
 X-ray Pulses to Spectrum

spectrum

charge
staircase slow amplifier

analog-to- energy bins

collects e-h
digital
as charge
converter

fast amplifier

from Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 13
 Slow EDS Pulse Processing

● EDS can process only one photon at a time

» A second photon entering, while the first photon pulse
is being processed, will be combined with the first
photon
» Photons will be recorded as the sum of their energies fast amplifier

● X-rays entering too close in time are thrown

away to prevent recording photons at incorrect
energies
slow amplifier
● Time used to measure photons that are thrown
away is “dead time”
» Lower dead time -> fewer artifacts
» Higher dead time -> more counts/sec into spectrum slower amplifier

● Processor extends the “live time” to

compensate

Counting is linear up to 3000 cps

(20-30% dead time)

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 14
 Things for Operator to Check

● Detector Performance
» Energy resolution (stamped on detector)
» Incomplete charge collection (low energy tails)
» Detector window (thin window allows low-energy x-ray detection)
» Detector contamination (ice and hydrocarbon)
» Count rate linearity (counts vs. beam current)
» Energy calibration (usually auto routine)
» Maximum throughput (set pulse processor time constant to collect the
most x-rays in a given clock time with some decrease in energy resolution)

Topics in red explained in next few slides

PASI - Electron Microscopy - Lyman - EDS Qual 15

 Energy Resolution

● Natural line width ~2.3 eV (Mn Kα )

» measured full width at half maximum (FWHM)

● Peak width increases with statistical

distribution of e-h pairs created and electronic
noise:

2 2 1/ 2
FWHM » (C E + N )
C = 2.35(Fe)1/ 2
E = x-ray energy
N = electronic noise
F = Fano factor (~0.1 for Si)
● Measured with 1000 cps at 5.9 keV
»
E K= 3.8
Mn α
eV/electron-hole pair
line

Mn Kα line

from Williams and Carter, Transmission Electron

Microscopy, Springer, 1996.
PASI - Electron Microscopy - Lyman - EDS Qual 16
 X-ray Windows

● Transmission curve for a

“windowless” detector
» Note absorption in Si

● Transmission curves for

several commercially
available windows
» Specific windows are better
for certain elements

from Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003.
PASI - Electron Microscopy - Lyman - EDS Qual 17
 Ice Build Up on Detector
Surface
● All detectors acquire an ice layer Windowless
over time detector
» Windowless detector in UHV
acquires ~ 3µm / year
● Test specimens Immediately
after warmup
» NiO thin film (Ni Lα / Ni Kα )
» Cr thin film (Cr Lα / Cr Kα )
After operating
● Check L-to-K intensity ratio for
1 year
Ni or Cr
» L/K will decrease with time
as ice builds up
» Warm detector to restore
(see manufacturer) Courtesy of J.R. Michael

PASI - Electron Microscopy - Lyman - EDS Qual 18

 Spectrometer Calibration

● Calibrate spectrum using two known

peaks, one high E and one low E
» NiO test specimen (commercial)
– Ni Kα (high energy line) at 7.478 keV
– Ni Lα (low energy line) at 0.852 keV
» Cu specimen
– Cu Kα (high energy line) at 8.046 keV
– Cu Lα (low energy line) at 0.930 keV

● Calibration is OK if peaks are within 10

eV of the correct value

● Calibration is important for all EDS

software functions 0.930 keV 8.046 keV

from Goldstein et al., Scanning Electron Microscopy and

X-ray Microanalysis, Springer, 2003.

PASI - Electron Microscopy - Lyman - EDS Qual 19

 Artifacts in EDS Spectra
●
Si "escape peaks”
Si Ka escapes the detector
» Carrying 1.74 keV
» Small peak ~ 1% of parent
» Independent of count rate
»

●
Sum peaks
Two photons of same energy enter detector simultaneously
» Count of twice the energy
» Only for high count rates
»

●
Si internal fluorescence peak
Photon generated in dead layer
» Detected in active region
»

from Williams and Carter, Transmission Electron Microscopy,

Springer, 1996
PASI - Electron Microscopy - Lyman - EDS Qual 20
 Expand Vertically to See EDS
Artifacts

Escape peaks

Si
interna
l fluor.

System Sum
peaks peaks

from Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Springer, 2003.

PASI - Electron Microscopy - Lyman - EDS Qual 21

 EDS-TEM Interface

Usually fixed by manufacturers of EDS and TEM

● We want x-rays to come from just under the electron probe, BUT…

● TEM stage area is a harsh environment

» Spurious x-rays, generated from high energy x-rays originating from
the microscope illumination system bathe entire specimen
» High-energy electrons scattered by specimen generate x-rays
» Characteristic and continuum x-rays generated by the beam
electrons can reach all parts of stage area causing fluorescence

● Detector can't tell if an x-ray came from analysis region or from

elsewhere

PASI - Electron Microscopy - Lyman - EDS Qual 22

 The Physical Setup

● Want large collection angle, Ω

» Need to collect as many counts
as possible
● Want large take-off angle, α
» But Ω reduced as α is
increased
● Compromise by maxmizing
Ω with α ~ 20˚ at 0˚ tilt angle
» can always increase α by tilting
specimen toward detector -- but
this increases specimen
interaction with continuum from
specimen

from Williams and Carter, Transmission Electron Microscopy, Springer, 1996

PASI - Electron Microscopy - Lyman - EDS Qual 23

 Orientation of Detector to
Specimen
● Detector should have clear
view of incident beam hitting
specimen
» specimen tilting eucentric
» specimen at 0˚ tilt

● Identify direction to detector

within the image EDS
detector
● Analyze side of hole
"opposite the detector” Rim
Edge of hole
Thinned
● Keep detector shutter closed furthest from
until ready to do analysis detector

t or
from Williams and Carter, Transmission
etec
Electron Microscopy, Springer, 1996 D
Top view of disc
PASI - Electron Microscopy - Lyman - EDS Qual 24
 Spurious X-rays in the
Microscope
● Pre-Specimen Effects
» spurious x-rays => hole count due to column x-rays and stray
electrons
» spurious x-rays => poor beam shape from large C2 aperture
● Post-Specimen Scatter
» system x-rays => elements in specimen stage, cold finger,
apertures, etc.
» spurious x-rays => excited by electrons and x-rays generated in
specimen
● Coherent Bremsstrahlung
» extra peaks from specimen effects on beam-generated
continuous radiation

The analyst must understand these effects to achieve

acceptable qualitative and quantitative results
PASI - Electron Microscopy - Lyman - EDS Qual 25
 Test for Spurious X-rays
Generated in TEM
● Detector for x-rays from
illumination system
Beam-generated Electron
» thick, high-Z metal acts as
Spurious (bad) Ni K x-ray (good) beam
“hard x-ray sensor"
● Uniform NiO thin film used to Mo K-series
normalize the spurious "in hole"
counts, thus NiO film on C Hole
» NiO film on Mo grid*

Ι ον
ΜοΚ
ΝιΟ φιλµ

% hole count = α
ον ΝιΟ φιλµ ξ 100%
Ι ΝιΚ
α
Mo grid bar
(Νοτε
- “on film”:results
∀ον ΝιΟ φιλµresults
~ “in hole” χουντ∀ανδ
∀ιν ηολεχουντ∀αρε σιµιλαρ
)
- Usually take inverse “hole count” ratio
Hard x-ray from
illumination system

* see Egerton and Cheng, Ultramicroscopy 55 (1994) 43-54

PASI - Electron Microscopy - Lyman - EDS Qual 26

 Spectrum from NiO/Mo

Measure in center of grid

square on NiO/Mo specimen Maximize
P/B ratio
● Spurious x-rays for Ni Kα
» Inverse hole count
(Ni Kα / Mo Kα )
» Want high inverse
hole count
● Fiori P/B ratio
» Ni Kα /B(10 eV)
» Increases with kV
» Want high to
improve element Minimize spurious Mo x-rays
detectability by using thick C2 aperture

Egerton and Cheng, Ultramicroscopy 55 (1994) 43-54

PASI - Electron Microscopy - Lyman - EDS Qual 27

 Figures of Merit for an AEM
● Fiori PBR = full width of Ni Kα divided by 10 eV of background
● (Ni Kα ) / ( Mo Kα ) is inverse hole count

Better

Less good

Obviously, we want to use the highest kV

from Williams and Carter, Transmission

Electron Microscopy, Springer, 1996
PASI - Electron Microscopy - Lyman - EDS Qual 28
 Beam Shape and X-ray
Analysis
● Calculated probes (from Mory, 1985)

C2 aperture too large

correct C2 aperture size

“witch’s hat” beam tail

excites x-rays

● Effect on x-ray maps (from Michael, 1990)

Properly limited Spherically aberrated

PASI - Electron Microscopy - Lyman - EDS Qual 29
 Qualitative
Analysis
Which elements are present?

● Collect as many x-ray counts as possible

» Use large beam current regardless of poor spatial resolution with
large beam
» Analyze thicker foil region, except if light elements x-rays might be
absorbed

● Scan over large area of single phase => avoid spot mode

● Use more than one peak to confirm each element

PASI - Electron Microscopy - Lyman - EDS Qual 30

 Qualitative Analysis Setup 1

Specimen
» Use thin foils, flakes, or films rather than self-supporting disks to reduce spurious x-rays (not
always possible)

» Orient specimen so that EDS detector is on the side of the specimen hole opposite where you
take your analysis

» Collect x-rays from a large area of a single phase

» Choose thicker area of specimen to collect more counts

» Tilt away from strong diffracting conditions

– (no strong bend contours)

» Operate as close to 0˚ tilt as possible (say, 5˚ tilt toward det.)

PASI - Electron Microscopy - Lyman - EDS Qual 31

 Qualitative Analysis Setup 2

Microscope Column
» Use highest kV of microscope
» Use clean, top-hat Pt aperture in C2 to minimize “hole count”
effect
» Minimize beam tails
– (C2 aperture or VOA should properly limit beam angle)
» Use ~ 1 nA probe current to maximize count rate
– This may enlarge the electron beam (analyze smaller regions
later)
» Remove the objective aperture

PASI - Electron Microscopy - Lyman - EDS Qual 32

 Qualitative Analysis Setup 3

X-ray Spectrometer
» Ensure that detector is cranked into position
» Keep detector shutter closed until you are ready to analyze
» Use widest energy range available (0-20 keV is normal)
– 0–40 keV for Si(Li) detector
– 0–80 keV for intrinsic Ge detector
» Choose short detector time constant (for maximum countrate)
» Count for a long time – 100-500 live sec

PASI - Electron Microscopy - Lyman - EDS Qual 33

 Peak Identification

● Start with a large, well-separated, high-energy peak

» Try the K-family
» Try the L-family
» Try the M-family
– Remember -- these families are related
● Check for EDS artifacts
● Repeat for the next largest peak

● Important:
» Use more than one peak for identification
» If peak too small to "see", collect more counts or forget about
identifying that peak; peak should be greater than 3B1/2

PASI - Electron Microscopy - Lyman - EDS Qual 34

 Chart of X-ray Energies (0-20 keV)
from Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Springer, 2003

M-series

L-series

K-series

PASI - Electron Microscopy - Lyman - EDS Qual 35

 Chart of X-ray Energies (0-5 keV)
from Goldstein et al., Scanning Electron Microscopy and X-ray Microanalysis, Springer, 2003

M-series

L-series

K-series

PASI - Electron Microscopy - Lyman - EDS Qual 36

 Know X-ray Family Fingerprints

PASI - Electron Microscopy - Lyman - EDS Qual 37

 Some Peaks will Look Similar

At low energies each

series collapses to a
single line M-series

From 1 keV to 3 keV, the

K, L, or M lines all look
Z
similar L-series

At 2.0 keV:
Z = 15 (P) Kα @ 2.013 keV K-series
Z = 40 (Zr) Lα @ 2.042
Z = 77 (Ir) Mα @ 1.977

after Goldstein et al., Scanning Electron Microscopy

and X-ray Microanalysis, Springer, 2003
PASI - Electron Microscopy - Lyman - EDS Qual 38
 Unknown #1

Energy (keV)
PASI - Electron Microscopy - Lyman - EDS Qual 39
 Data Analysis for Unknown #1

26
4.5 6.4
Fe(26)
Kα
4.9 7.0
Fe(26)
Kβ

PASI - Electron Microscopy - Lyman - EDS Qual 40

 Unknown #1

from xray.optics.rochester.edu/.../spr04/pavel/

PASI - Electron Microscopy - Lyman - EDS Qual 41

 Unknown #2

after www.pentrace.com/ nib030601003.html

PASI - Electron Microscopy - Lyman - EDS Qual 42
 Analysis of Unknown #2

Line Energy(keV) Int, Sh Candidate 1 Candidate 2

1 0.2 w C(6) K (0.25)
2 0.8 vw Ru(44) Lα escape (0.86) Ni(28) La (0.8)
3 1.4 w, sym W(74) Mζ (1.4)
4 1.8 s, sym W(74) Mα (1.8) No possible K line

5 2.6 m, asym Ru(44) Lα (2.6)

6 6.4 w, sym Fe(26) Kα (6.4)
7 7.1 vw Fe(26) Kβ (7.1)
8 7.4 m, sym W(74) Ll (7.4) Ni(28) Ka (7.5)
9 8.0 vw Cu(29) Kα (8.0) Ni(28) Kb (8.3)
10 Start 8.3 m, sym W(74) Lα (8.4) No possible K line

11 9.6 m, overlap W(74) Lβ 1 (9.7)

12 10.0 m, overlap W(74) Lβ 2 (10.0)
13 11.3 w, sym W(74) Lγ 1 (11.3)
14 11.6 vw W(74) Lγ 3 (11.6)

PASI - Electron Microscopy - Lyman - EDS Qual 43

 Qualitative Analysis

W Mα
Elements present
major: W, Ru
trace: Fe, Cu, C

W Lα
Ru Lα
W Mζ W Ll
Fe Kα ,β W Lβ 1,2

C Cu W Lγ 1,3

PASI - Electron Microscopy - Lyman - EDS Qual 44

 Automatic Qualitative Analysis?

Check the results of every automatic qualitative analysis

1. Are suggested elements reasonable?

Tc and Pm are unusual, Cl and S are not

2. Do not use peak energy alone to identify

Lines of other elements may have the same energy

3. Consider logic of x-ray excitation

All lines of an element are excited in TEM/STEM (100-300 kV)
If L-series indicated, K-series must be present
If M-series indicated, L-series must be present

PASI - Electron Microscopy - Lyman - EDS Qual 45

 Automatic Qualitative
Analysis Blunders

Identification by peak energy alone Identification without considering

without considering x-ray families other lines of same element
or peak shape

from Newbury, Microsc. Microanal. 11 (2005) 545-561

PASI - Electron Microscopy - Lyman - EDS Qual 46

 Summary
● EDS in the TEM has more pitfalls than in SEM
» Use the highest kV available
» Understand the effects of:
– detector-specimen geometry
– spurious x-rays from the illumination system
– post-specimen scatter
– beam shape and spatial resolution => the “witch’s hat”
● Identify every peak in the spectrum
» Even artifact peaks
» Forget peaks of intensity < 3 x (background)1/2
● Collect as many counts as possible
» Use large enough beam size to obtain about 1 nA current
» Qualitative analysis use:
– use long counting times or
– thicker electron-transparent regions with a short pulse processor time constant,
if appropriate
» Assume data might be used for later quantitative analysis (determine t if
possible)

PASI - Electron Microscopy - Lyman - EDS Qual 47