Do Minh Nghiep

Materials Science Center

Electron Microscopy
and Diffraction
7. X-Ray Elemental Microanalysis

Part of the figures, texts are quoted from internet resources. All the copyrights belong to the original authors.
All the references made here are for educational purpose only.
 Content
• Origin of X-rays
• Characteristic radiation-discontinuum
spectrum
• Bremstrahlung-continuum spectrum
• Energy Dispersive Spectroscopy (EDS)
• Wavelength Dispersive Spectroscopy (WDS)

21.05.10 2
X-rays
 Origin of X-rays
 An inelastic collision
between a primary beam
electron and an inner
orbital electron results in
the emission of that
electron from the atom.
 The energy released
from an electron
replacement event
produces a photon with
an energy exactly equal
to the drop in energy.
21.05.10 4
 Primary X-rays

X-rays can have

an energy nearly
equal to that of the
primary beam
electron and thus
can escape from
very deep within
the specimen.

21.05.10 5
Secondary X-rays: fluoresence

E-atom
interaction

Xray-atom
interaction

21.05.10 6
 Fe-K family

When an electron from a K-shell is When an electron from a K-shell is

replaced by one from the next replaced by one from the second
closest shell (L), it is designated as closest shell (M), it is designated
a Kα event. as a Kβ event.
21.05.10 7
 Fe-L family
 When an electron from a
L-shell is replaced by one
from the next closest shell
(M), it is designated as a
Lα event.
 The K shell will never
donate its electron as this
would require an increase
in energy, not a drop.

21.05.10 8
System of spectrum lines

Certain events such

as Mα, Lβ, and Kγ
are only possible in
atoms of sufficient
atomic weight (N-
shell).

21.05.10 9
System of spectrum lines
There are actually
a wide variety of
subsets of these
X-rays, since each
electron shell has
multiple orbitals.
Example:
K-shell (1), L-
shell (3), M-shell
(5) ...
21.05.10 10
Bremstrahlung-continuum spectrum

Bremsstrahlung X-rays
are the major part of
the continuum X-ray
signal that can escape
from the deepest
portion of the
interaction region.

21.05.10 11
Continuum spectrum

"Bremsstrahlung" means "braking radiation" and comes from the original

German to describe the radiation which is emitted when electrons are
decelerated or "braked" when they interact with the specimen. Although
they contribute to the total X-ray signal, they contain no useful information,
because their energies are nonspecific and therefore are considered as part
of the background: Eo = E + Ei (mv2/2 = E + hC/λ ).
21.05.10 12
 Origin of
continuum spectrum

Because E = Eo-Ei different,

energy of X-ray photons Ei
changes continuously from
E0 > E1 > E2 > E3 >…>
En
(λ o<λ 1<λ 2<λ 3<...<λ n)

21.05.10
13
 X-ray
spectroscopy
21.05.10 14
 Two X-ray spectrometers for
microanalysis by EDS and WDS
y pocs ort ce p S
gr e n E: S DE

21.05.10 15
 How X-rays are collected
in EDS and WDS

EDS: by Si detector WDS: by monocrystal

21.05.10 16
 EDS
histogram

X-ray
Histograms

WDS
histogram

21.05.10 17
 Energy
Dispersive
Spectroscopy
(EDS)
21.05.10 18
 Principal scheme of EDS

21.05.10 19
 Semi-
conductor
detector and
spectrum
measurement

21.05.10 20
 Construction of detector system

 Collimator to limit BSE and stray X-

rays
 Window usually made of beryllium
(limited to sodium, atomic number 11)
or thin plastic to detect down to boron
(atomic number 5) protects cooled
crystal from air.
 Detector crystal silicon wafer with lithium added in. For each 3.8 eV from
an X-ray, produce an electron and hole. This produces a pulse of current,
the voltage of which is proportional to the X-ray energy. Must keep the
crystal at Liquid Nitrogen temperature to keep noise to a minimum.
21.05.10 21
Expanded view of an EDS detector

21.05.10 22
Elements of semiconductor detector

Lithium doped silicon (SiLi) crystal detector acts as a

semiconductor that carries current in a rate proportional to
the number of ionization events and acts as an indirect
measurement of the energy contained in the X-ray.
21.05.10 23
Function of semiconductor detector

Each ionized atom

of silicon absorbs
3.8 eV of energy,
so an X-ray of 3.8
keV will ionize
approximately
1000 silicon atoms.

21.05.10 24
Factors affecting signal collection

 Distance between detector and X-ray source,

 Angle at which detector is struck,
21.05.10  Volume of signal collected. 25
Factors affecting signal collection:
take-off angle

ϕ : take-off
angle
(góc thoát tia)

For a given angle of electron incidence, the length of the absorption

path is directly proportional to the cosecant of the take-off angle, φ
21.05.10 26
 Factors affecting signal collection:
solid angle

Ω: solid angle
(góc chiếu)

The solid angle Ω of a detector is defined as angle of the

cone of signal entering the detector. The greater the size of
the detector surface area (or the closer to the source) the
21.05.10
greater will be the solid angle. 27
How to increase solid and take-off angles

 One can also increase the solid angle by placing the detector closer to
the source.
 One then tries to maximize both the solid angle and the take-off angle.
21.05.10 28
 Semiconductor detector

One reason that the final lens of an SEM is conical in shape is so that
the EDS detector can be positioned at a high take-off angle and inserted
21.05.10 close to the specimen for a high solid angle. 29
 Characteristics of detector

(Ω)

Larger SiLi crystals will be able to sample a larger volume of signal

(better Ω), but because of imperfections in the crystal they have
slightly greater noise and thus slightly lower resolution.
21.05.10 30
 Multi-channel analyzer: MCA

Then Now
MCA consists of an analog to digital converter which “scores” the
analog signal coming from the field effect transistor (FET). Newer
systems employ a digital pulse processor which converts the signal on
the fly.
21.05.10 31
 An EDS histogram

The changes in conductivity of the SiLi crystal can be counted for a

given time and displayed as a histogram using a multichannel analyzer.
21.05.10 32
Qualitative analysis by EDS/EDX

Positive identification of an element is best done by collection of the

21.05.10 entire family of peaks for a given element. 33
# Counts X-ray spectrum

X-ray energy in keV

 An X-ray spectrum for a sample is composed of all

the possible signals for that given set of elements.
 These will differ in terms of energies (keV) and
probabilities (likelihood) scored as number of such
signals collected over a given period of time.
21.05.10 34
X-ray emission and absorption energy (keV)

Each element has a family of characteristic X-rays associated with it

21.05.10 35
Example 1: Asbestos materials

EDS histogram of
Chrysotile Asbestos Fibers

SE image of
Chrysotile Asbestos Fibers Chemical composition of
(sợi amiăng) the fibers: Si, Mg and Fe
21.05.10 36
 Example 2:
Gunshot Residue (GSR) analysis

Bullet fragments (blue, vết đạn)

can be identified on cloth fibers
and distinguished from other
metal pieces by their elemental
composition.

BSE image of EDS histogram

cloth fibers of cloth fibers

21.05.10 37
 GSR
(Gunshot
Residue-GSR)

Gunshot Residue (GSR) analysis: criminal

investigation by elemental analysis of GSR,
identifying a gun firing
21.05.10 38
 GSR
(Gunshot Residue)

Gunshot Residue (GSR)

analysis:
 Particles are very characteristic,
therefore presence of these
particles forms evidence of firing
a gun.
 Particles normally consist of Pb
(lead), Sb (antimony) and Ba
(barium).
 New ammunition: environmentally
friendly (no Sb).
21.05.10 39
 GSR
(Gunshot Residue)
 The proportion of
elements present in
GSR differ slightly and
databases of GSR from
different manufacturers
can be used to identify
what ammunition was
used in a crime.
 GSR is often found on
criminals and also on
victims if shot at close
range.

21.05.10 40
 X-Ray elemental mapping

Ca Al Si

S K Mg

21.05.10 Fe Na BEI 41
 Elemental maps

SEI

21.05.10 42
Analysis of painting materials

Combined with
backscatter
imaging (BSEI)
Au and X-ray maps of
Au (a), Ba (b) and
Ca (c) different
layers of paint can
Ba Ca be identified.

21.05.10 43
 Wavelength
Dispersive
Spectroscopy
(WDS)
21.05.10 44
 Diffraction in crystals

William Henry Bragg Like an electron beam an X-ray has

1862 – 1942 its own wavelength which is
Nobel Prize in Physics
1915
proportional to its energy.
21.05.10 45
 Crystal detector

Crystal: A solid formed

by the solidification of a
chemical and having a
highly regular atomic
structure. May be
composed of a single
element (C / diamond) or
multiple elements
(BaTiO3).
21.05.10 46
 Close packing
of crystals
HÖ s¸u ph­
¬ng

Cubic Hexagonal

21.05.10 47
Vulf-Bragg’s law of diffraction

If a wavelength enters a crystal at the appropriate angle it will be

diffracted rather than being absorbed or scattered by the crystal.
21.05.10 48
 Diffraction law

For a given wavelength λ there is a specific angle θ (Bragg’s angle) at which

diffraction will occur. Bragg’s angle is determined by the d-spacing
(interplanar spacing) of the crystal and the order of diffraction (n = 1, 2, 3….).
21.05.10 49
 Crystal detector

A WDS detector takes advantage of the fact that an X-

ray of a given wavelength can be focused by a crystal
if it encounters the crystal at the proper Bragg’s angle.
21.05.10 50
 Crystal-monochromator

Focused Non-focused

To better accomplish this crystals are bent and ground to form a

curved surface which will bring all the diffracted X-ray wavelengths
to a single focal point, thus the crystal acts as a focusing lens.
21.05.10 51
 Crystal-monochromator

Rawland Rawland
circle circle

To change the Bragg’s angle the diffracting crystal and

detector can be moved together relative to the stationary
specimen along a circle known as the Rowland Circle.
21.05.10 52
Wavelength Dispesive Spectrometer

Rawla
nd
circle

21.05.10 53
 WD
spectrometer

WDS detectors are quite large and must be positioned around the specimen chamber
at an angle to take advantage of maximum take-off angle and maximum solid angle.
21.05.10 54
An electron probe microanalyzer EPMA
(Multi-channel EDS and WDS)

21.05.10 55
An electron probe microanalyzer EPMA

A Microprobe is a specialized SEM that is outfitted with an EDS

detector and array of several WDS detectors.
21.05.10 56
 Crystals for detector
 Different diffracting crystals can
only diffract certain wavelengths
(even with the changes in Bragg’s
angle).
 So an array of detectors must be
used if one is to be able to detect
K, L, and M events for many
different elements.
 Since WDS detectors do not
need to be cooled they are
windowless and can detect down
to Berylium
LiF - Lithium fluoride, PET - Pentaerythritol, and TAP - Thallium acid phthalate
21.05.10 57
How to chose a crystal-monochromator

21.05.10 58
 Specimen preparation for WDS

 Samples must be conductive since high

keV is used (carbon coating if not
naturally conductive).
 Samples must be flat (polished) as
geometry of sample to detector is crucial
and also minimizes artifacts when doing
quantitative measurements.

21.05.10 59
 WDS vs EDS
Characteristics WDS EDS

Spectral resolution, eV high: 2-6 low: 130-155

Collection efficiency low (slower) high (faster)

Ration P/B (peak/background) higher lower

Effect of sample geometry highly sensitive to low sensivity

geometric effects
Spectral artifacts few several

Liquid nitrogen no required required / LN-free

Moving mechanical parts Yes no / yes

Beam current relatively high lower feasible

typical
Purchase very expensive less expensive

21.05.10 60
WDS vs
EDS
in
SEM

21.05.10 61
Comparison of EDS and WDS

21.05.10 62
 (Ba-Lα + Ti-

WDS vs EDS
Kα )

BaTiO3

 A comparison of two spectra

collected with EDS and WDS
shows how peak overlap and
energy spread can serve to
Ti-Kα 1,2 obscure the information in an
Ba-Lα 1,2
EDS spectrum.

 EDS: overlaping, Ba and Ti

BaTiO3 can’t resolved
 WDS: no overlaping, better
resolution

21.05.10 63
 Elemental
quantitative analysis

21.05.10 64
 Calculation formular
N spec
Cspec = .Cstd = k .Cstd
N std
Cspec , Cstd - concentration of specimen and standard
Nspec , Nstd - peak intensity of specimen and standard
k - correction factor

21.05.10 65
 Quantitative X-ray analysis

If one wants to quantify the relative amounts of different elements

present in a complex sample one has to account for a number of
factors and carry out a correction of the data
21.05.10 66
 Correction factor ZAF

Several methods to correct the spectra. ZAF takes into account

the Atomic Weight (Z), effects of Absorbance (A) and effects of
Fluorescence (F) in adjusting the data to give the correct values.
21.05.10 67
 Correction of overlaping

As

Cd

One must account for other elements present in the sample and whether
their individual peaks overlap with each other creating a “shoulder” that
can mask the presence of one element or distort the midpoint of another.
21.05.10 68
EDS microanalysis in STEM mode

EDS can be added as a component of a TEM. It requires an angled

detector (for take-off angle) and scan coils in the column to function
as a Scanning Transmission Electron Microscope or STEM.
21.05.10 69
 Application of
EDS in STEM

EDS can be used to identify

elements present vacuoles
or inclusions. Must take
into account elements
present in the embedding
medium.

21.05.10 70
 Application of EDS and WDS
 X-ray microanalysis enables the SEM and TEM to
be used as analytical instruments.
 Limitations include the quantities of given element
and an inability to distinguish isotopes.
 By placing a focussed beam over an object allows
one to carry out microchemical analysis on very
small or very discrete objects or to map the
presence of various elements within a specimen.

21.05.10 71
Element
linescan

21.05.10 72
Application
- diffusion
zone

21.05.10 73
Some elemental analysis techniques

21.05.10 74
Some elemental analysis techniques

21.05.10 75