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An Analytical Technique: Pixe
An Analytical Technique: Pixe
AN ANALYTICAL TECHNIQUE
PIXE PARTICLE-INDUCED
X-RAY EMISSION
CHARGED PARTICLE
USUALLY PROTONS OR OTHER
IONS
Basic Principle
Brief history
As early as 1912, Chadwick used particles
from a radioactive source to induce X-ray
emission, but with such a low intensity that it
was not possible to study any details of
emission process or to use it for analytical
purposes.
The foundation laid in 1914 by Moseley in his
pioneering study of energy of the
characteristic X-ray lines of different
elements of periodic table. He used a flat
crystal spectrometer with photographic
recording.
Photographic plate of X-ray spectra
recorded by Moseley in 1914
Brief history
In 1922 Swedish geologist HADDING
reported on the analysis of various minerals.
He detected 10-12 elements in the samples
and made a comparison with the result of
analysis performed with conventional
chemical methods.
A great step forward in X-ray emission
spectrometry was made when CASTAING at
the University of Paris in 1950 showed that X-
rays emitted by the specimen could be
exploited for multi-elemental analysis.
Brief history
In
1950, when accelerators become
available in connection with the rapid
growth of nuclear physics research
considerable interest in investigating
the X-ray emission process had been
started with their help.
Brief history
During the 1960’s, a great progress was
made in nuclear detector technology Solid-
State Surface Barrier detector were
developed for charged particles. For energy
dispersive spectrometry of X-rays the
lithium-drifted silicon detector, Si (Li)
become available. It has an energy resolution
of about 150 eV measured for 5.9 keV X-ray,
which make it possible to resolve K X-rays
from adjacent elements.
Brief history
In 1970, Johansson et al. at Lund
Institute of Technology showed that a
combination of excitation with 2 MeV
proton and X-ray detection with Si (Li)
detector constituted a powerful method
for multi-elemental, non-destructive
analysis of trace elements.
Brief history
In1980’s this new analytical method
which soon become known under the
acronym PIXE was tested and applied
in many nuclear physics labs. There are
several reasons for its rapid growth
and development in 90’s onward.
Brief history
The growing interest in environmental
problems created a need for efficient method
of trace elemental analysis. Air pollution
studies and the determination of toxic
elements in environment and humans are
analyzed by PIXE.
Small Accelerators become available in many
nuclear physics labs.
A third reason for the interest in PIXE was
the development of micro beam Technique.
Such a beam has many interesting
applications.
Brief history
It is probably fair to say that PIXE has
now reached a stage of maturity. A
good picture of the development of
PIXE can be obtained from International
PIXE conferences starting from 1977,
which are arranged every third year.
The proceedings of these conferences
illustrate the increasing use of PIXE in
various scientific fields.
X-ray production process
X-ray production process
RADIATIVE TRANSITION
Characteristic X-ray
• K-series
• L-series
• M-series
NON RADIATIVE TRANSITION
Aüger effect
Coster-Krönig transition
Notations for X-ray spectrum
Energy of K and L X-rays as a function of
atomic number
Instrumentation
Beam preparation
Collimators
On demand deflection plates.
Beam current measurements
Visual inspection of the beam at
various points using quarts viewers
whose fluorescent can be seen.
External beam PIXE.
Experimental setup
External beam PIXE setup
Instrumentation
Choice of spectrometer
Si (Li) & HPGe
HPGe has advantages of maintaining
effectively approximately 100%
efficiency well beyond 25 keV photon
energy at which this quantity begins to
fall off in Si (Li) detector.
Si (Li) detector efficiency
Typical PIXE spectrum
Analytical Analysis
Energy Calibration
Absolute Comparison
Method Method
with standard
Comparison
PIXE BASICS
• For an incident proton energy of 1 – 4 MeV,
elements with atomic numbers up to about 50
are generally determined through their K X-rays
(typically Kα line). Heavier elements are
measured through their L X-rays because the
energies of their K X-rays are too high to be
detected by using the Si(Li) detector available
commercially.
• The concentration of an element is deduced from
the intensity of the measured X-ray line together
with parameters obtained either theoretically
and/or experimentally.
Quantitative analysis
Absolute method
Requirement of different parameters.
Generalized geometry.
Generalized geometry of PIXE analysis of
specimen
The X-ray yield
Yu = 4 • Np• nz• su• eu
Where
= solid angle subtended by the detector at the target,
Np = number of incident protons that hit the specimen,
nz = number of sample atoms per unit area of the specimen Z
Z= is the atomic number of the element,
su = production cross-section for u - line x-rays,
eu = detection efficiency for u - line x-rays.
Areal concentration of an analysed element
The concentrations of the analysed elements are usually
what one wants to obtain from a PIXE measurement. For
thin specimens, the areal concentration (i.e. mass/unit
area) is often the quantity of interest .
Qp = 1.60210 x 10-13 x Np μC
Direct Np determination methods
These methods involve charge integration carried
out in various ways.
• Use of a Faraday cup coupled to a charge
integrator.
Charge
integrator
Proton beam Faraday cup
Specimen
Proton beam
Beam chopper
Specimen
Charge integrator
Indirect Np determination methods
A common method is by measuring the back-scattered
protons from the specimen.
Proton beam
Specimen
Particle detector
Proton beam
su = sS • wS • ru
where
sS = S-shell ionization cross section (S = K, L, M, …),
wS = fluorescence yield,
ru = fractional radiative width of u-line X-rays.
The ionization cross-section sS
sS is a probability factor and has the dimensions of area. The
product nz• ss represents the probability for a proton to knock
off a s-shell electron from a target atom.
Area = ss
1 cm
1 cm
Determination of sS
sS is a function of incident proton energy and can be
determined theoretically. Three different theoretical
approaches have been used to calculate the cross
sections for inner-shell vacancy creation:
• the binary encounter approximation (BEA),
• the semi-classical approximation (SCA),
• the plane wave Born approximation (PWBA).
Theoretical cross sections for K-shell ionization with
protons calculated with PWBA are found to be in good
agreement experimental data and are adequate for
most PIXE work. For the case of L-shell ionization, the
situation is much less favorable.
The fluorescence yield
n 1
l = ±1
j = ±1 or 0
1 2
g1
b2 b1 b3 b4
L
Detection efficiency e
where
No • su
yu =
4 • (1.60210 x 10-13) • Az
FORMULA FOR DETERMINING AREAL
CONCENTRATION
By re-arranging the equation in the previous slide ,
we have the following formula which can be used to
determine the areal concentration of an element in a
thin specimen.
Yu
mz =
• Qp• eu • yu
Cl CaK
1000
PS
WL
FeK
K CaKb
WLb
X-ray counts
100 TiK
X-ray counts
WLb
FeKb
WLg
TiKb
WL l
10
1
2 4 6 8 10 12 14
collected by
detector over
Time
a short time.
Conversion to digital (ADC)
• The voltage signal
from the detector
must be digitized
before it can be
stored in the
computer. The curve
is integrated to find
the area.
Conversion to digital (ADC)
• The area under the
curve is measured
and is converted to a
digital number. This
number is a measure
of the energy of the
X-ray seen by the
detector.
Histograms
• The number from the ADC is collected and
stored in a histogram – a collection of bins (we
use 2048) scaled to match the energy spectrum
of the X-rays we want to measure.
Histograms
• As the ADC gives the number for the X-ray
energy, the count in the appropriate bin is
incremented, and over time the shape of the
distribution begins to develop.
Typical Spectrum (INCO 625)
• Here’s a histogram from a run on one of our standards,
INCO 625. There are lots of peaks here.
Equation for concentration of given element in
a specimen
Yx z N avwbe i NpCzs x z
4
Yx z : X-ray yield
: Solid angle
N av : Avogadro number
4
w : Fluorescent yield
Np : Number of protons
C z Specimen Yz Specimen
C z S tan dard Yz S tan dard
• Detection Limits
Detectable concentration as a function of
atomic number and proton energy in a typical
PIXE arrangement
Application
Air Pollution
Micro PIXE
Proton Microprobe
Applications of mapping in different
areas
Micro PIXE setup
Proton microprobe arrangement
PIXE elemental maps from a bone
3-dimensional element plot from micro PIXE
analysis of single cell
3 MeV PIXE elemental maps of Ag, Cu and Si seen on
the surface of fragment of lusterware from 9th century
Iraq
Example of direct PIXE analysis of human
finger nail
Thank you