PIXE –

AN ANALYTICAL TECHNIQUE

DR. HARSH MOHAN

DEPARTMENT OF PHYSICS
M.L.N. COLLEGE
YAMUNA NAGAR
(HARYANA)
 Contents
 INTRODUCTION
 BASIC PRINCIPLE
 BRIEF HISTORY
 X-RAY PRODUCTION PROCESS
 INSTRUMENTATION
 ANALYTICAL ANALYSIS
 APPLICATION
 NEW AVENUES
 Introduction

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

Qualitative Analysis Quantitative 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

The number of counts under the X-ray peak

corresponding to the principal characteristic X-
ray line of an element is called the yield (Yu ) for
the u - line. It is a product of 5 quantities:


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 .

This quantity (denoted by mz) is related to nz (the

number of element atoms per unit area) by the
equation:
Az • nz
mz =
No

where Az = atomic mass of the sample element,

No = Avogadro’s number (6.02252 x 1023).
 DETERMINATION OF Np

The knowledge on the number of protons that

hit the specimen in a PIXE measurement is
required for quantitative PIXE analysis. Np can
be measured directly or indirectly.
As protons are positively charged, Np is often
measured by charge integration and quoted in
units of micro-Coulombs (or μC). The charge
carried by a proton is 1.60210 x 10-19 Coulombs.
The charge carried by Np protons is therefore:

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

This is only suitable when the specimen is not

thick enough to stop the proton beam. For thick
and conducting specimen, one may couple the
charge integrator directly to the specimen holder.
 Direct Np determination methods

• Use of rotating vane or chopper which periodically

intercepts and samples the proton beam.

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

One may obtain Np by measuring the number of protons back-

scattered from a thin film (carbon is often used).

Thin carbon film

Proton beam

Particle detector Specimen

 X-ray production cross-section su

su is a product of three factors:

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

Following the ejection of an electron from an inner

atomic shell through the ionization process, the
vacancy in this particular atomic shell is quickly
filled by an electron from an outer shell. Such an
electron transition will lead to the emission of
either a characteristic X-ray or an Auger electron.
The probability of the X-ray emission alternative is
known as the fluorescence yield.
Although the fluorescence yield can be calculated
theoretically, experimental data are usually used in
PIXE analysis.
 The K-shell fluorescence yield

The K shell of an atom is a single shell and has no

sub-shell. Therefore K-shell fluorescence yield of an
atom is simply:
Ik
wk =
Nk
where Ik is the total number of K x-rays emitted from a
sample and Nk is the number of K shell vacancies.
 The L-shell fluorescence yield
The definition of fluorescence yield for the L shell (or any higher
shell) is more complicated because of the Coster Kronig transition
(non-radiative transition between sub-shells). The L shell has 3
sub-shells (LI, LII and LIII), and Coster Kronig transitions can occur
between LI and LII, between LI and LIII, or between LII and LIII. A
Coster Kronig transition will result in shifting a vacancy from a
lower-energy sub-shell to a higher-energy sub-shell with in the
shell

An electron from an outer shell may

occupy a vacancy in any of the 3 L
sub-shells.
III
L II Coster Kronig transitions
I
 The fractional radiative width ru

Electron transitions in the atomic de-excitation are

governed by the following “selection rules”:

n  1
 l = ±1
 j = ±1 or 0

Where n, l and j are the principle, the orbital angular

momentum and the total angular momentum quantum
numbers respectively. Although “forbidden transitions” are
observed but their probabilities are usually very small and
not of any significant. The electron that fills up the vacancy
in a particular inner shell may come from one of the many
outer shells allowed by the selection rules, but with
different probabilities which are often referred to as
fractional radiative widths.
 K X-ray lines
The K X-ray lines come from electron transitions that finish at the
K shell. The partial energy level diagram below shows the origin
of the main K X-ray lines: By convention, an X-ray line is
denoted by a leading capital letter
indicating the final shell involved in
VII the transition followed by a small
N | Greek letter and a numeric subscript
I
to reflect the intensity of the line
V relative to the others (for example
M |
I
K1). 1 is the strongest line, 2 the
next and followed by b1 etc. In x-ray
spectra obtained using Si(Li)
L II
III
detectors, the  sub-lines and the b
I sub-lines usually appear as two
lines because the energies of the
1 2 b1 b3 b2 sub-lines are too close to be
K resolved. Hence, these two lines
are often referred to simply as K
line and Kb line.
 L X-ray lines
The L X-ray lines come from electron transitions that finish
on the L shell. The partial energy level diagram below
shows the origin of the principle L X-ray lines:

1  2
 g1

b2 b1 b3 b4

L
 Detection efficiency e

The detection efficiency of a Si(Li) X-ray

detector is dependent on the X-ray
energy. It is usually determined
theoretically using the parameters (i.e.
thicknesses of Si diode, Be window, gold
contact and Si dead layer) provided by
the detector manufacturer. However,
calibration standards are often used to
determined e experimentally.
Qualitative analysis Isotope Energy
in keV
55Fe 5.864
 Energy and efficiency
6.485
using different
57Co 6.371
isotopes.
7.024
14.361
241Am 11.861
13.936
17.727
20.766
26.305
RELATION BETWEEN X-RAY YIELD AND AREAL
CONCENTRATION

The expression for Yu introduced earlier can

be written as:
Yu =  • Qp• mz• eu• yu

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

Note that yu can be computed theoretically and is the

yield per mC of charge per unit areal concentration per
steradian for 100% detection efficiency.
 Use of filters
In PIXE measurements of intermediate and thick specimens, the
bremsstrahlung background can be large, especially in the low-
energy region. This will bring about poorer detection limits for
the detection of light elements as well as diminish the sensitivity
for the detection of medium- and high-z elements. To reduce the
low-energy background, a plastic or metal filter of appropriate
thickness are often placed between the specimen and the
detector.
If a filter is used, one must correct for its effect of x-ray
attenuation in calculating the concentration of an element. Thus
the equation for cz becomes:
Yu
cz =
 • Qp• eu • yu • fT

where fT is the transmission factor of the filter, which

is a function of X-ray energy.
A PIXE spectrum consists of two components:
peaks due to characteristic X-rays, & a background continuum,
as can been seen from the spectrum shown below, which is
obtained from a lung tissue taken from a patient suffered
from hard metal lung disease:

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

X-ray energy (keV)

X-ray energy (kev)
PIXE spectrum of the above tungsten rich area
 Output from detector
• X-ray hits
detector,
produces lots
of charge,
which is Voltage

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

b : Line intensity Cz : Concentration of element

ei : Efficiency of the detector s x z  : X-ray production cross-section

Comparison with standards

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

PIXE spectrum of air pollution collected on a thin foil

 Application
 Industrial application

K X-ray spectra recorded for (a) 4x10-11 g of Ti, (b) 8x10-10 g of Cu

 Application
Botany

PIXE spectrum from analysis of Shaji plant material

 Application
 Archeology

PIXE spectrum of potshred (broken piece of pot)

 Application
 Art

PIXE external beam setup for analysis of an art document

 Application
 Medical science

PIXE analysis of Bromine

in blood plasma
 New Avenues

 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