Introduction to X-Ray

Fluorescence (XRF) Analysis

MSE 854
Dr. Sofia Javed
September 2021
 Luminiscence
• A process of giving light
THE ELECTROMAGNETIC SPECTRUM
How does light affect molecules and atoms?

D.C. Harris, Quantitative Chemical Analysis, 7th Ed., Freeman, NY, 2007.
 X-RAY INTERACTIONS WITH MATTER
When X-rays encounter matter, they can be:

• Absorbed or transmitted through the sample

(Medical X-Rays – used to see inside materials)

http://www.seawayort.com/hand.htm

• Diffracted or scattered from an ordered crystal

(X-Ray Diffraction – used to study crystal structure)

http://commons.wikimedia.org/wiki/File:X-ray_diffraction_pattern_3clpro.jpg

• Cause the generation of X-rays of different “colors”

(X-Ray Fluorescence – used to determine elemental composition)
 Type of information obtained by
X-ray material interaction
Incident X-rays
Scattered X-ray
(Crystal structure
chemical
identification: XRD) Characteristic X-rays
(elemental analysis:XRF)
Electron:
Photoelectron spectroscopy(XPS)
Surface analysis

Transmitted X-rays
(X-ray machine: non destructive testing)
 ATOMIC STRUCTURE

• An atom consists of a nucleus (protons and neutrons) and electrons

• Z is used to represent the atomic number of an element
(the number of protons and electrons)
• Electrons spin in shells at specific distances from the nucleus
• Electrons take on discrete (quantized) energy levels (cannot occupy
levels between shells
• Inner shell electrons are bound more tightly and are harder to remove
from the atom
Adapted from Thermo Scientific Quant’X EDXRF training manual
 ELECTRON SHELLS
Shells have specific names (i.e., K, L, M) and
only hold a certain number of electrons

The shells are labelled from the

nucleus outward

K shell - 2 electrons

L shell - 8 electrons

M shell - 18 electrons
N shell - 32 electrons

X-rays typically affect only inner shell (K, L) electrons

Adapted from Thermo Scientific Quant’X EDXRF training manual

MOVING ELECTRONS TO/FROM SHELLS
Binding Energy versus Potential Energy

• The K shell has the highest binding

energy and hence it takes more energy
to remove an electron from a K shell
(i.e., high energy X-ray) compared to an
L shell (i.e., lower energy X-ray)

• The N shell has the highest potential

energy and hence an electron falling
from the N shell to the K shell would
release more energy (i.e., higher energy
X-ray) compared to an L shell (i.e., lower
energy X-ray)

Adapted from Thermo Scientific Quant’X EDXRF training manual

 XRF – A PHYSICAL DESCRIPTION
Step 1: When an X-ray photon of sufficient energy strikes an atom, it dislodges an electron
from one of its inner shells (K in this case)

Step 2a: The atom fills the vacant K shell with an electron from the L shell; as the electron
drops to the lower energy state, excess energy is released as a K X-ray

Step 2b: The atom fills the vacant K shell with an electron from the M shell; as the
electron drops to the lower energy state, excess energy is released as a K X-ray

Step 1:

Step 2b:

Step 2a:

http://www.niton.com/images/XRF-Excitation-Model.gif
 XRF – SAMPLE ANALYSIS

http://www.niton.com/images/fluorescence-metal-sample.gif

• Since the electronic energy levels for each element are different, the
energy of X-ray fluorescence peak can be correlated to a specific element
 SIMPLE XRF SPECTRUM

400
As K line
10.53 keV

300
Intensity (cps)

200
As K line
11.73 keV

100

0
0 5 10 15 20 25 30 35 40

Energy (keV)

• The presence of As in this sample is confirmed through observation of two peaks

centered at energies very close (within ±0.05 keV) to their tabulated (reference) line
energies
• These same two peaks will appear in XRF spectra of different arsenic-based materials
(i.e., arsenic trioxide, arsenobetaine, etc.)
 SIMPLE XRF SPECTRUM

700
Pb L line Pb L line
10.55 keV 12.61 keV
600

500
Intensity (cps)

400

300

200

100

0
0 5 10 15 20 25 30 35 40
Energy (keV)

• The presence of Pb in this sample is confirmed through observation of two peaks

centered at energies very close (within ±0.05 keV) to their tabulated (reference) line
energies
• These same two peaks will appear in XRF spectra of different lead-based materials (i.e.,
lead arsenate, tetraethyl lead, etc.)
 BOX DIAGRAM OF XRF INSTRUMENT
X-ray Digital Pulse XRF Results
Source Detector Spectrum (elements
Processor software
(cps vs keV) and conc’s)

Sample
• X-ray tube source
High energy electrons fired at anode (usually made from Ag or Rh)
Can vary excitation energy from 15-50 kV and current from 10-200 A
Can use filters to tailor source profile for lower detection limits

• Detector (SDD(Silicone Drift Detector)) and digital pulse processor

Energy-dispersive multi-channel analyzer –detector monitors both the energy and number
of photons over a preset measurement time
The energy of photon in keV is related to the type of element
The emission rate (cps) is related to the concentration of that element

• Analyzer software converts spectral data to direct readout of results

Concentration of an element determined from factory calibration data, sample thickness as
estimated from source backscatter, and other parameters
X-Ray Source
 Braking radiation)

I = AiZV2
cont
 Wavelength Dispersive XRF
• A wavelength dispersive
detection system
physically separates the
X-Rays according to
their wavelengths.
• The x-rays are directed
to a crystal, which
diffracts the X-Rays in
different directions
according to their
wavelengths (energies).
 Energy Dispersive XRF

Intensity,
(conc.)

Energy(keV)= Element

• When a sample is irradiated by primary X-rays, the

flourescent X-ray generates ---detected by semiconductor
detector
• The kind of element is identified from the energy(horizontal
axis) and the conc. of element is calculated from X-ray
intensity (vertical axis)
 FOUR KEY ADVANTAGES OF XRF
FOR MANY APPLICATIONS
SIMPLICITY
• Relatively simple theory, instrument, and spectra (versus IR, MS, NMR)

MINIMAL SAMPLE PREP

• For many screening applications, samples can often be analyzed “as is” with minimal
sample processing
• For accurate quantitative analysis, samples must be ground up and homogenized
(faster and easier than processiong required for conventional atomic spectrometry
methods)

TYPICAL ANALYSIS TIMES ON THE ORDER OF 1 MINUTE

• For determining % levels of an element (which typically gives high count rates),
measurement times can be as short as a few seconds
• For ppm-level detection limits, measurement times on the order of 1-10 minutes are
needed

PORTABILITY
• Instrument can be brought to the samples
 SIMPLE XRF SPECTRUM

700
Pb L line Pb L line
10.55 keV 12.61 keV
600

500
Intensity (cps)

400

300

200

100

0
0 5 10 15 20 25 30 35 40
Energy (keV)

• The presence of Pb in this sample is confirmed through observation of two peaks

centered at energies very close (within ±0.05 keV) to their tabulated (reference) line
energies
• These same two peaks will appear in XRF spectra of different lead-based materials (i.e.,
lead arsenate, tetraethyl lead, etc.)
 XRF – MORE DETAILED DESCRIPTION
Note energy level diagrams are not drawn to scale

As Pb
∞ ∞

N 4s2p3d10f14 N 4s2p3d10f14
L 12.55 keV
M 3s2p3d10 M 3s2p3d10
K 11.73 keV
L 10.61 keV
As Pb
L 2s2p6 L 2s2p6
>15.21 keV
(absorption edge)

K 10.53 keV

K 1s2 K 1s2
>11.86 keV http://www.niton.com/images/fluorescence-metal-sample.gif

(absorption edge - minimum amount of energy needed to remove electron)

• Since XRF affects inner shell and not bonding electrons, the XRF spectrum of an element is
independent of its chemical form (i.e., spectra of lead, lead arsenate, and tetraethyl lead
will ALL show peaks at 10.61 and 12.55 keV)
X-ray Transition Energy Database
http://physics.nist.gov/PhysRefData/XrayTrans/Html/search.html
 ADVANTAGES OF XRF

Selectivity: True multi-element analysis (from Be to Am)

Measures total element concentration (independent of chemical form)

Detection limits: 1 to 10 ppm at best (depends on source, element, matrix, etc.)

Linearity: Linear response over 3 orders of magnitude (1-1000 ppm)

Precision: Relative Standard Deviation < 5% (must have homogeneous sample)

Speed: Minimal sample prep (analyze “as is” or homogenize and transfer to cup)
Fast analysis times (typically seconds to minutes)

Miscellaneous: Simple (can be used by non-experts in the field)

Nondestructive (sample can be preserved for follow up analysis)
Field-portable instruments can operate under battery power for several hours
 LIMITATIONS OF XRF

Selectivity: Interferences between some elements (high levels of one element may give a false
positive for another due to overlapping emission lines and limited resolution of ~0.2
keV FWHM)

No info on chemical form of element (alternate technique required for

specification)

Detection Must use alternate technique to measure sub-ppm levels

Limits:

Accuracy: XRF is predominantly a surface analysis technique (X-rays penetrate few mm into
sample)

To get more accurate results, one must homogenize the samples and calibrate
instrument response using authentic standards