Energy-Dispersive X-ray

Microanalysis in the TEM

Anthony J. Garratt-Reed
Neil Rowlands
One result of the interaction of an
electron beam with matter is the
emission of x-rays
One result of the interaction of an
electron beam with matter is the
emission of x-rays
The energy and wavelength of the X-
rays is different for, and characteristic
of, each element
One result of the interaction of an
electron beam with matter is the
emission of x-rays
The energy and wavelength of the X-
rays is different for, and characteristic
of, each element
Analysis of the X-rays can, therefore,
be used as a tool to give information
about the composition of the sample
In today's talk:
In today's talk:
i. X-ray emission from materials
In today's talk:
i. X-ray emission from materials
ii. X-ray detectors (brief!)
In today's talk:
i. X-ray emission from materials
ii. X-ray detectors (brief!)
iii. Quantitative chemical analysis
In today's talk:
i. X-ray emission from materials
ii. X-ray detectors (brief!)
iii. Quantitative chemical analysis
iv. Spatial Resolution
X-ray emission from
materials
X-ray emission from
materials
2 independent processes
X-ray emission from
materials
2 independent processes
Characteristic X-rays (discrete
energies)
X-ray emission from
materials
2 independent processes
Characteristic X-rays (discrete
energies)
Bremsstrahlung (continuum)
Characteristic X-rays
2-step process involving the atomic
electrons
Characteristic X-rays
2-step process involving the atomic
electrons
Firstly, the atom is excited by ionization of
one of the core-level electrons
Characteristic X-rays
2-step process involving the atomic
electrons
Firstly, the atom is excited by ionization of
one of the core-level electrons
This is followed by an outer-shell electron
losing energy by emission of a photon (the
X-ray), and dropping to the core state
Bremsstrahlung
Braking radiation
Bremsstrahlung
Braking radiation
All charged particles radiate energy when
accelerated
Bremsstrahlung
X-ray detectors
X-ray detectors
Lithium-drifted Silicon (Si(Li))

X-ray detectors
Lithium-drifted Silicon (Si(Li))
Used since around 1970 on SEMs
X-ray detectors
Lithium-drifted Silicon (Si(Li))
Used since around 1970 on SEMs
Silicon Drift detector

X-ray detectors
Lithium-drifted Silicon (Si(Li))
Used since around 1970 on SEMs
Silicon Drift detector
Over the last 5 years
X-ray detectors
Lithium-drifted Silicon (Si(Li))
Used since around 1970 on SEMs
Silicon Drift detector
Over the last 5 years
Crystal detectors Electron Microprobe
X-ray detectors
Lithium-drifted Silicon (Si(Li))
Used since around 1970 on SEMs
Silicon Drift detector
Over the last 5 years
Crystal detectors Electron Microprobe
Different characteristics
Si(Li) crystal
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
About 3mm thick and 3-6 mm diameter
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
About 3mm thick and 3-6 mm diameter
Electrodes plated on front and back
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
About 3mm thick and 3-6 mm diameter
Electrodes plated on front and back
Front electrode is thin to allow X-rays to
enter
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
About 3mm thick and 3-6 mm diameter
Electrodes plated on front and back
Front electrode is thin to allow X-rays to
enter
Biased by a voltage of 3-500V
Si(Li) crystal
Crystal of pure silicon, with lithium diffused
in to compensate for any residual carriers
About 3mm thick and 3-6 mm diameter
Electrodes plated on front and back
Front electrode is thin to allow X-rays to
enter
Biased by a voltage of 3-500V
Cooled to Liq. N
2
Si(Li) crystal
Energy of an x-ray generates electron-
hole pairs
Si(Li) crystal
Energy of an x-ray generates electron-
hole pairs
These are swept from the crystal by the
bias voltage, and are detected in the
external circuitry as a pulse of charge
Si(Li) crystal
Energy of an x-ray generates electron-
hole pairs
These are swept from the crystal by the
bias voltage, and are detected in the
external circuitry as a pulse of charge
Since the average energy required to
create an electron-hole pair is constant and
predictable (about 3.8eV), the external
charge is proportional to the x-ray energy
Quantitative Analysis
Quantitative Analysis
Different techniques for:
Quantitative Analysis
Different techniques for:
SEM
Quantitative Analysis
Different techniques for:
SEM
Organic thin sections
Quantitative Analysis
Different techniques for:
SEM
Organic thin sections
Materials thin sections
Quantitative Analysis
Different techniques for:
SEM
Organic thin sections
Materials thin sections Today's talk!
Characteristic X-rays
2-step process involving the atomic
electrons
Firstly, the atom is excited by ionization of
one of the core-level electrons
This is followed by an outer-shell electron
losing energy by emission of a photon (the
X-ray), and dropping to the core state
Characteristic X-rays
2-step process involving the atomic
electrons
Firstly, the atom is excited by ionization of
one of the core-level electrons
This is followed by an outer-shell electron
losing energy by emission of a photon (the
X-ray), and dropping to the core state -
Fluorescence
Ionization cross-section

Ionization cross-section
The Ionization cross-section is defined as
the probability of ionizing a single atom in a
region of uniform current density of
electrons.
Ionization cross-section
The Ionization cross-section is defined as
the probability of ionizing a single atom in a
region of uniform current density of
electrons.
Usually denoted by Q
A
where the A
denotes the particular element of interest

Ionization cross-section
The Ionization cross-section is defined as
the probability of ionizing a single atom in a
region of uniform current density of
electrons.
Usually denoted by Q
A
where the A
denotes the particular element of interest
It has units of area
Ionization cross-section
Units are generally Barns, where
1 Barn=10
-24
square centimeters
Ionization cross-section
Units are generally Barns, where
1 Barn=10
-24
square centimeters
Typical values of the cross-section are
100-1000 Barns.
Ionization cross-section
Units are generally Barns, where
1 Barn=10
-24
square centimeters
Typical values of the cross-section are
100-1000 Barns.
For practical purposes, the cross-section
can be regarded as a function of the
electron energy alone, and is independent
of the chemical surroundings.
Ionization cross-section
For practical purposes, the cross-section
can be regarded as a function of the
electron energy alone, and is independent
of the chemical surroundings.
Various equations have been proposed to
predict the value of the ionization cross-
section for all the elements at different
beam voltages
Characteristic X-rays
2-step process involving the atomic
electrons
Firstly, the atom is excited by ionization of
one of the core-level electrons
This is followed by an outer-shell electron
losing energy by emission of a photon (the
X-ray), and dropping to the core state -
Fluorescence
Fluorescence Yield
Fluorescence Yield
Generally given the symbol e
A
where,
again, the subscript A denotes the
particular element.
Fluorescence Yield
Generally given the symbol e
A
where,
again, the subscript A denotes the
particular element.
For practical purposes again, the
fluorescence yield can be considered to be
a constant for a particular transition. (No
significant dependence on chemical
bonding, for example)
Fluorescence Yield
For practical purposes again, the
fluorescence yield can be considered to be
a constant for a particular transition.
The fluorescence yield has been
measured for a wide range of lines; an
equation has been developed to fit these
measurements to predict the fluorescence
yield in those cases where measurements
have not been made.
Putting this together --
Putting this together --
We can write, for a sample of thickness t
and density :



where I
A
is the number of x-rays generated, i
p
is the probe
current in Amps, e is the electron charge, C
A
is the
concentration (weight fraction) of element A in the sample,
A
A
is the atomic weight of element A, s is a partition function
to account for the fraction of x-rays in the detected line, and
t is the analysis time in seconds.
t e =
A A A A
p
A
o
A
s Q C t
e
i
A
N
I
Writing the same equation for
element B and dividing:
B
A
B B B B
A A A A
A
B
B
A
C
C
s Q
s Q
A
A
I
I

=
c e
c e
Writing the same equation for
element B and dividing:
or
B
A
B B B
A A A
A
B
B
A
C
C
s Q
s Q
A
A
I
I

=
e
e
AB
B
A
B
A
k
C
C
I
I
. =
Since the detector sensitivity c
varies for different elements,
where the Is are now the
measured x-ray intensities for the
various elements
AB
B
A
B
A
B
A
k
C
C
I
I
.
'
'
c
c
=
Since the detector sensitivity c
varies for different elements,
where the Is are now the
measured x-ray intensities for the
various elements
AB
B
A
B
A
B
A
k
C
C
I
I
.
'
'
c
c
=
The Cliff-Lorimer equation
Limitations of Cliff-Lorimer
Valid for thin samples only
Limitations of Cliff-Lorimer
Valid for thin samples only
Limitations of Cliff-Lorimer
Valid for thin samples only
The more common reality!
Limitations of Cliff-Lorimer
Valid for thin samples only
Variations of detector parameters (espec.
ice)
Limitations of Cliff-Lorimer
Valid for thin samples only
Variations of detector parameters (espec.
ice)
Only works when all elements can be
detected
Limitations of Cliff-Lorimer
Valid for thin samples only
Variations of detector parameters (espec.
ice)
Only works when all elements can be
detected
Spectral Processing
Limitations of Cliff-Lorimer
Limitations of Cliff-Lorimer
Valid for thin samples only
Variations of detector parameters (espec.
ice)
Only works when all elements can be
detected
Spectral Processing
Spurious effects -
Spurious effects:
Fluorescence
Spurious effects:
Fluorescence
Escape peaks

Spurious effects:
Fluorescence
Escape peaks
Coherent Bremsstrahlung
Spurious effects:
Fluorescence
Escape peaks
Coherent Bremsstrahlung
Detector imperfections
Spurious effects:
Fluorescence
Escape peaks
Coherent Bremsstrahlung
Detector imperfections
Etc., etc.
Limitations of Cliff-Lorimer
Limitations of Cliff-Lorimer
Valid for thin samples only
Variations of detector parameters (espec.
ice)
Only works when all elements can be
detected
Spectral Processing
Spurious effects
Statistics!
Statistics
Counting of x-rays is a random
phenomenon
Why do we need counts?
2 sec, low count rate
Why do we need counts?
10 secs, low count rate
Why do we need counts?
100 secs, low count rate
Why do we need counts?
100 secs, high count rate
Statistics
Counting of x-rays is a random
phenomenon
In counting N events, there is an
uncertainty o (the standard deviation) which
is equal to the square root of N
Statistics
Counting of x-rays is a random
phenomenon
In counting N events, there is an inherent
uncertainty o (the standard deviation) which
is equal to the square root of N
N has a 95% probability of being within +-
2o of the Correct answer
Statistics
N has a 95% probability of being within +-
2o of the Correct answer
Hence if 1% precision is required 95% of
the time, 40,000 counts must be acquired
Statistics
N has a 95% probability of being within +-
2o of the Correct answer
Hence if 1% precision is required 95% of
the time, 40,000 counts must be acquired
Likewise for 0.1% precision, 4,000,000
counts are required
Statistics
Likewise for 0.1% precision, 4,000,000
counts are required
Approximately half the counts are in the
major peak of an element, so 8,000,000
counts must be acquired in the spectrum

Statistics
Likewise for 0.1% precision, 4,000,000
counts are required
Approximately half the counts are in the
major peak of an element, so 8,000,000
counts must be acquired in the spectrum
Maximum count rate for Si(Li) detector is
about 30,000cps, so this will take about 250
seconds (SDD will count at 250,000 cps)
Spatial Resolution
Spatial Resolution
Spatial Resolution
There is no single definition of Spatial
Resolution
Spatial Resolution
There is no single definition of Spatial
Resolution
Analyzing a small particle on a thin support
film has very different requirements from
analyzing a diffusion gradient in a foil
Spatial Resolution
There is no single definition of Spatial
Resolution
Analyzing a small particle on a thin support
film has very different requirements from
analyzing a diffusion gradient in a foil
Consider the diffusion example:
Spatial Resolution
Putting this together --
We can write, for a sample of thickness t
and density :



where I
A
is the number of x-rays generated, i
p
is the probe
current in Amps, e is the electron charge, C
A
is the
concentration (weight fraction) of element A in the sample,
A
A
is the atomic weight of element A, s is a partition function
to account for the fraction of x-rays in the detected line, and
t is the analysis time in seconds.
t e =
A A A A
p
A
o
A
s Q C t
e
i
A
N
I
But
( )
3
2
3
8
2
4
s
p
C
B d
i
t
=
(B is brightness of electron source, C
s
is spherical
aberration coefficient of objective lens)
Source Brightness:
Source Brightness:

Inherent function of emitter
Source Brightness:

Inherent function of emitter
Thermionic W: 5 V
o
A/cm
2
/Sr
Source Brightness:

Inherent function of emitter
Thermionic W: 5 V
o
A/cm
2
/Sr
Thermionic LaB6: 200 V
o
A/cm
2
/Sr
Source Brightness:

Inherent function of emitter
Thermionic W: 5 V
o
A/cm
2
/Sr
Thermionic LaB
6
: 200 V
o
A/cm
2
/Sr
Field Emitter: 5000 V
o
A/cm
2
/Sr




AND
Beam Broadening:

2 / 3
2 / 1
5
10 25 . 6 t
A E
Z
b
o

|
.
|

\
|
=

Spatial Resolution
AND
Beam Broadening:

2 / 3
2 / 1
5
10 25 . 6 t
A E
Z
b
o

|
.
|

\
|
=

Inserting values:
Z=26 (Iron), =8gm/cc, A=56, t=4E
-6
cm (40 nm),
E
o
=200KV

We find that b= 2.4x10
-7
cm (2.4 nm)
Optimizing,
We can estimate a spatial resolution of
about 2 nm with 1% analytical precision

Optimizing,
We can estimate a spatial resolution of
about 2 nm with 1% analytical precision
Or, much better resolution if the required
precision is not so high

Optimizing,
We can estimate a spatial resolution of
about 2 nm with 1% analytical precision
Or, much better resolution if the required
precision is not so high
Requires VERY good sample! (e.g.
thickness of ~10nm)