Electron Probe Microanalysis

EPMA

Related Topics:
X-ray Fluorescence (XRF)
and Synchrotron Radiation
Revised 5/23/2014
 What’s the point?
We utilize the x-rays produced by the electron microprobe for
many research applications.
There are other techniques, similar in some ways, that are worth
discussing, that utilize x-rays for secondary x-ray fluorescence.
Two in particular are:
• XRF (X-Ray Fluorescence), where x-rays from a sealed tube are
used to produce x-rays by secondary fluorescence in samples of
interest (traditionally a macro-technique)
• Synchrotron Radiation, where electrons are accelerated in ~10s-
100s meters diameter rings, and then made to produce highly
focused beams of extremely intense x-rays or light, which are
then fed into many different types of experiments.
The benefits of secondary x-ray fluorescence include very low
detection limits (10s of ppm easy in 10 seconds, no backgrounds)
 XRF Basics
The basics of XRF are very similar to those of EPMA—we are
dealing with characteristic x-rays and continuum x-rays— with
the exception that we are doing secondary fluorescence : x-ray
spectroscopy of our samples using x-rays coming out of a sealed
tube to excite the atoms in our specimen.
The big difference is that
• there is NO continuum generated in the sample (x-rays can’t
generate the Bremsstrahlung), and
• we are using BOTH characteristic x-rays of the sealed tube
target (e.g., Cr, Cu, Mo, Rh) AND continuum x-rays to generate
the characteristic x-rays of the atoms in the sample.
XRF has been a bulk analytical tool (grind up 50-100 grams of
your rock or sample to analyze), though recently people are
developing “micro XRF” to focus the beam on a ~100 m spot.
 X-ray Sources

The standard X-ray tube (top right) was

developed by Coolidge (at GE) around
1912.
It is desirable to produce the maximum
intensity of x-rays; a Cu target tube might
be able to deliver 2 kW. The limiting
factor is the heat that the target (anode)
can handle; cold water is used to remove
heat.
Higher power can be delivered by
dissipating the heat over a larger volume,
with a rotating anode (bottom right).
However, this is not normally used for
XRF.

* Power in watts = current [amps] x voltage [volts] From Als-Nielsen and McMorrow, p. 31
 X-ray Attentuation

characteristic
T
A
X-ray R
G
E
T (Compton)

(Rayleigh)

This figure shows the attenuation of the X-rays in the target (sample).
In addition to photoelectric absorption (producing characteristic X-rays and
photoelectrons [includes Auger electrons]), the original X-rays may be
scattered.
There are two kinds of scattering: coherent (Rayleigh) and incoherent
(Compton).
 X-ray Scattering
Coherent (Rayleigh) scattering happens
when the X-ray collides with an atom and
deviates without a loss in energy. An electron
in an alternating electromagnetic field (e.g. X-
ray photon), will oscillate at the same
frequency (in all directions).
It essentially becomes a small radiating dipole, Coherent
scattering the incident energy in all directions
at the same frequency of the X-ray.
This is useful for understanding X-ray
(Rayleigh scattering also
diffraction (in depth).
explains why the sky is
This is elastic scattering – no loss of in energy. blue. Rayleigh scattering
has a strong inverse
One impact in XRF is that the X-ray line of the dependence on the
X-ray source may be “backscattered” off of the wavelength of the radiation.
sample onto the detector and show up as So the shorter wavelength
something present in the sample. blue light is scattering more
than other colors.)
 X-ray Scattering
Incoherent (Compton) scattering is where
the incident X-ray loses some of its energy to
the scattering electron. It is inelastic scatter.
As total momentum is preserved, the
wavelength of the scattered photon increases
by the equation
(in Å)
where is the scatter angle. Since  is near Incoherent
90°, there will be an addition peak from the
main tube characteristic peak at about 0.024Å
higher wavelength
 Compton Scattering - YouTube

There is a nice You Tube explanation of Compton

Scattering at
https://www.youtube.com/watch?v=fI2C4VlR1OM
 Compton Scattering Peaks

The top figure shows a wavelength

spectrum of the Mo Ka peak from the x-
ray tube (P=primary, Mo Ka).
The other 3 figures show the splitting of
the primary Mo Ka peak into a Compton
Scattering Peak due to the incoherent
scattering in an Al target, and the effect of
changing the scattering angle.

From Liebhafsky et al, 1972

 Continuum of X-ray Tube in XRF
Secondary fluorescence by x-rays in the sample does not
produce continuum x-rays there. However, the continuum is
produced within the selected x-ray tube which is the “gun” in
XRF.
This continuum is of interest here as it is useful for excitation
source in XRF.
Kramers (1923) deduced the relationship between continuum
intensity, wavelength and atomic number of the x-ray source
(“target”):

where the x-ray intensity I is a function of x-ray tube current i, Z

is the mean Z of the target and min is the E0 equivalent.
 Kramers Law and Continuum Intensity

Some comments:
From Williams, Fig 2.2

• for maximum XRF counts,

you want to maximize your
current (I) and minimize your
min which is to say 12.4/E0 …
or… run at the highest
accelerating voltage your x-ray
tube can handle (40-50 keV)
• obviously, the higher the Z of • finally, Kramers Law is
the target in the tube, the sometimes used in EPMA
higher the counts for theoretically modelling
the Bremsstrahlung there
 An EDS spectral comparison: XRF vs SEM
XRF XRF-EDS* SEM-EDS

Why do these look so different from our “normal” EDS view of

a spectrum?
Why is there a ‘whale-like’ hump at the high energy end?
And not on the EDS spectrum?
* Highly simplified
 Explanation: XRF vs SEM EDS – part 1
XRF XRF-EDS* SEM-EDS

This question has stumped me for years. In the past 6 months, I’ve had 2
people who saw this slide on the web, ask me to explain it. Here’s the best
explanation I can come up with: it stems from the fundamental differences
between processes. EDS in SEM is a 2 step process (electrons from W-
filament hit unknown sample, whose x-rays are generated) vs a 3 step
process in XRF (electrons from W-filament hit a [say Mo] metal target
[anode], then all those x-rays (continuum plus Mo characteristic) hit the
unknown sample, whose x-rays [=Secondary Fluorescence] are generated
including Compton-scattering peaks from the (say) Mo anode.
 Explanation: XRF vs SEM EDS – part 2
XRF XRF-EDS* SEM-EDS

The middle figure is hokey in that it doesn’t show the characteristic peaks of
the sample (e.g. like the O, Ti and Fe peaks of the ilmenite in the SEM-
EDS), only the anode’s peaks (much less the Compton peaks that would be
there). Whatever. The W-filament in say a Rh-anode X-ray tube might be
run at 66 keV, which means there will be the characteristic plus Compton Rh
Ka-Kb peaks around 22 keV as well as continuum x-rays out of the x-ray
tube up to 66 keV, able to excite the unknown specimen. Let’s look at a
REAL XRF spectrum (OK, it’s WDS, but it’s real and we’ll flip it around in
our heads into EDS space.)
 Explanation: XRF vs SEM EDS – part 3

Here is the high energy end of an actual XRF spectrum; most of the elements
being analyzed are off the screen to the right, and we see here the Rh K lines
plus their associated Compton peaks (“C”). To the left is a drop in the
background (absorption edge of ?) and then there is a more gradual drop off of
the background, not the dramatic one I copied out of textbooks. So I am
thinking that there are significant x-rays generated at energies higher than Rh
Kb (22.7 keV) because the original continuum coming off the Rh anode is
interacting with the specimen, but presumably the probability of X-rays is less
and less.
 Explanation: XRF vs SEM EDS – part

Actually, at the very far left lower part of the spectrum are some little
bumps…these are REE Ka and Kb peaks, but with extremely low P/B, so
unusable. So the spectrum doesn’t actually drop off a cliff at the high energy
end.

(Thanks to Maciej Sliwinski for assistance with is tough problem.)

OK, what do Compton scattering peaks look like? this is using a
Rh target….using a SiLi detector, so there is a Si-escape peak too),
energy increases to
the right.

(Shackley, 2011)
OK, what does an XRF spectrum REALLY look like… note, this
is using a Rh target)

(Shackley, 2011)
…and an expert refers to “Bremsstrahlung scattering does appear
at the heavy end of the spectrum” particularly useful for Ba in
volcanic rocks.

(Shackley,
2011)
 XRF spectrometer

An XRF spectrometer is
very similar to an electron
microprobe: just replace the
electron gun with an x-ray
tube located very close to
the specimen;both the
characteristic and the
continuum x-rays cause
(secondary) fluorescence of
the specimen, and the
resulting x-rays are focused
using collimators in either Fig 4-1 Williams
WDS (crystal + counter) or
EDS (solid state detector)
mode .
 A Currently Marketed XRF (WDS version)
This actual
model contains
additional
components.
There are
probably over a
dozen companies
building and
selling XRFs of
various designs.
In fact, two are
here in Madison:
Bruker-AXS
(~Siemens) and
ThermoNORAN
(microXRF) From Bruker-AXS brochure
 Sample Prep in XRF

Samples and standards (fine powders) are mixed with

a flux (e.g., a glass disk with ~90% LiBO4 for major
elements, a pressed pellet with ~75% cellulose for
traces).
The purpose is to minimize “particle size / micro-
absorption effects” by producing a more uniform
absorption path for samples made of discrete phases
that may not have been ground down into submicron
sizes.
 Correction of XRF Intensity Data

XRF intensity data (counts) is much simplier to

correct, compared with EPMA data:
• No Z (atomic number) correction
• No F (fluorescence) correction
• Only A (absorption) correction

Calibration curves are developed for each element.

 UW XRF Core Scanner
Stephen Meyers has one of these for chemically
mapping sediment cores.
 UW XRF Core Scanner
Application of the XRF Core Scanner: deep sea
sediments and search for chemical signature of cyclical
behavior in sediment deposition
 Synchrotron Radiation (SR) - Defined*
Synchrotron = particle (electron, proton, neutron) accelerator.
The particle orbits a track; acceleration is produced by an
alternating electric field that is in synchronism with orbital
frequency.
SR = electromagnetic radiation (e.g. radio waves, X-rays)
generated within a synchrotron, or through similar natural
process in deep space (e.g. some of strongest celestial radio
sources). Electrons or other charged particles moving in a
strong magnetic field field are forced to spiral around magnetic
lines of forces. If they travel near speed of light, they emit, in
direction of travel, a sharp beam of electromagnetic radiation
polarized normal to the direction of magnetic field. Whether
radiation appears as light or radio waves depends on its
frequency, which is determined by the electrons’ velocity.
* Encyclopedia Britannica, 1974
Synchrotron Setup

From Als-Nielsen and McMorrow

 Wigglers or Undulators and X-rays
Shown here is the cone of x-
rays generated by positrons
moving with near-speed-of-
light energy through an
insertion device. The array of
permanent magnets produces a
magnetic field that alternates
up and down along the positron
path, causing the particles to
bend back and forth along the
horizontal plane. At each bend,
the positrons emit synchrotron
radiation in the x-ray part of
the spectrum.

From The Advanced Photon Source at Argonne National Laboratory, October 1997 brochure
 Synchrotron X-ray Diffraction
In x-ray scattering experiments, an x-
ray beam is passed through a sample,
and the intensities and directions of
the scattered x-rays are measured. The
pattern of scattered x-rays is converted
by the computer into information
about the arrangement of atoms in the
sample.

From The Advanced Photon Source at Argonne National Laboratory, October 1997 brochure
 Synchrotron X-ray Microscopy
A monochromator and a pinhole are used to select the
coherent, laser-like part of an x-ray beam from an APS
undulator. This beam is then focused to a tiny spot by a
zone plate and directed at a sample being studied. As the
sample is scanned back and forth across the beam spot,
the x-rays transmitted through the sample are
recorded in a computer. The data are then
used to develop an image
showing the structure of the
sample

From The Advanced Photon Source at Argonne National Laboratory, October 1997 brochure
 Synchrotron X-ray Spectroscopy
A beam of x-rays passes through a
sample and a measurement is made
of the degree to which x-rays of
different energies are absorbed by
the sample. One type of x-ray
spectroscopy is called extended x-
ray absorption fine structure,
EXAFS. In EXAFS spectra, weak
oscillations indicate the effect of
scattering from neighboring atoms
by an electron ejected from the The weak oscillations in
atom that absorbs an x-ray. This EXAFS spectra can be
involves electron scattering effects, analyzed by computer models
rather than the x-ray scattering to infer the relative locations
effects described in the previous of atoms in the structure.
slide.
Advances with X-ray source brightness
with time…to 2001

UW-MSN SRC

From Als-Nielsen and McMorrow

 UW-Madison Synchrotron
Radiation Center (Stoughton)
In 1965 construction began on
the 240 MeV electron storage ring
Tantalus “for advanced accelerator
concepts” tests. But before its
completion in 1968, interest in
synchrotron radiation research
soared, and changes were made to
accommodate SR. And it then
became dedicated to SR, and here
many breakthroughs were made,
e.g., the superiority of the electron
storage ring as a source of SR was
first shown. In 1977, SRC began
construction on a new and much
larger SR source, Aladdin (1 GeV
storage ring). The SRC storage ring beamlines are optimal for ultrahigh
vacuum ultraviolet (vuv) and soft x-ray (sxr) research.
 UW-Madison SRC
Aladdin was constructed with 36 beam
ports, and 4 long straight sections for
insertion devices like undulators and
wigglers. There are 26 beamlines in
operation and 5 under development*.
The SRC serves the requirements for
many investigations, including:
• high resolution optical absorption spectroscopy
of solids and gases
• high resolution reflectance spectroscopy of
solids
• photoinduced luminescence in solids and gases • photoelectron diffraction
• photoabsorption, dissociation and ionization • x-ray lithography
cross section measurements • x-ray microscopy
• chemisorption and physisorption studies • intrared spectroscopy and
• modulation spectroscopy microscopy (FT-IR)
* 1996 literature quote.
 Resources for XRF and Synchrotron
Introduction to X-Ray Spectrometry by K. L. Williams,
1987, Allen & Unwin (covers both XRF and EPMA)
X-Rays, Electrons, and Analytical Chemistry by
Liebhafsky, Pfeiffer, Winslow and Zemany, 1972,
Wiley (title says it all)
Elements of Modern X-Ray Physics by Als-Nielsen and
McMorrow, 2001, Wiley
Synchrotron powder diffraction by L.W. Finger, in
Modern Powder Diffraction (Bish and Post, eds)
Reviews in Mineralogy Vol 20, 1989, Min. Soc. Am.
powerpoint talk on Synchrotron Radiation Sources and
Free Electron Lasers by Josef Frisch: posted to the
G777 web page (‘articles for discussion’)