Advanced instrumental techniques

for micro, surface and trace analysis

P. Van Espen
Dept. of Chemistry
University of Antwerp, Belgium
piet.vanespen@ua.ac.be
X-ray fluorescence analysis:
A general purpose trace analysis method
Course outline
1. Introduction
2. X-ray physics
3. Instrumentation
4. XRF Configurations
5. Quantitative analysis
X-ray Fluorescence (XRF)
Atoms in the sample are excited and emit characteristic x-rays
x-ray source
x-ray detector
Energy of characteristic x-rays
How does it work?
1. Introduction
concentration
(quantitative analysis)
Number of x-rays for each element
type of elements present
(qualitative analysis)
Fluorescence lines
Scatter Excitation
(Ag K-lines)
Continuum
Fe 3.38%
Cu 2950 ppm
Zn 6952 ppm
Pb 5532 ppm
0 5 10 15 20 25 30 35 40
600
1200
1800
2400
3000
3600
4200
4800
5400
keV
Counts
Pb
Sr
Rb Zr
Fe
Cu
Zn
Mn
Typical XRF spectrum
NIST SRM 2710 Montana Soil
Cd-109 source, Si(Li) detector
How do the x-ray spectra look?
1. Introduction
Analytical characteristics of XRF
instrumental analytical technique - multi-element capability
elemental analysis of solids and liquids
minimal sample treatment
concentration range: ppm to % (trace, minor and major elem.)
element range: from boron to uranium (in theory)
Why and when to use XRF?
Industrial process control (metallurgy, cement, glass, industry)
mining and exploration
geology and geochemistry
materials research
environmental analysis
archaeology
14 000 XRF instruments in operation world wide
1. Introduction
Types of XRF instruments
How can we classify XRF methods?
Based on the excitation
Tube excited XRF
Radio-isotope excited XRF
Secondary target,
Synchrotron,
Total reflection...
Based on the detection
Wavelength dispersive (WD-XRF)
Energy dispersive (ED-XRF)
Filter instruments (proportional counter)
1. Introduction
Historical background
1895: Wilhelm Conrad Roentgen
(University of Wrzburg)
discovery of X-rays while experimenting with
discharge tubes
X = unknown X-radiation or X-rays
1913: Coolidge
Demonstration of the possibility of XRF using a X-ray tube
1913: Moseley law
1948: Friedmann and Birks
First prototype wavelength-dispersive XRF spectrometer
1965: Lawrence Berkeley Laboratories, USA
Development of Si(Li) detectors, first energy-dispersive systems
1. Introduction
How did we got there we are now?
= K Z ( )
2
1. Introduction
Summary
What to remember from this?
1. in XRF x-rays are used to excite the sample
2. characteristic x-rays are measured in the form of a spectrum
3. the spectrum tells which elements are present and how much
4. element range: B U; concentration range ppm - %
5. used in various fields
6. there are wavelength and energy-dispersive instruments
X-ray are part of the electromagnetic spectrum between
ultraviolet radiation and gamma-rays.
The Nature of X-rays
When dealing with diffraction we best consider X-rays as
electromagnetic waves with wavelength
When discussing absorption and scattering of X-rays
they are best considered as
photons with a certain energy E.
h Planck's constant (6.6254x10
-34
J s)
c the velocity light the wave (3.00x10
8
m/s)
wavelength in meters
E Energy in joules.
Relation between energy and wavelength:

hc
= E
2. X-rays
What are x-rays?
Wavelength in ngstrom units (1 = 0.1 nm = 10
-10
m)
Energy in kilo-electronvolt (keV) 1 J = 6.24x10
15
keV
] [
4 . 12
[keV]

= E
Be K E = 0.11 keV = 113
Fe K E = 6.40 keV = 1.94
U K E = 98.4 keV = 0.126
X-rays in XRF
2. X-rays
What is the range of x-rays used in XRF?
Bohr approximation of the atom
The electrons in an atom occupy discrete energy levels.
electrons are grouped in shells designated K, L, M, N, O, P
(principal quantum number n = 1, 2, 3, 4, 5, and 6).
A shell can have at maximum 2n
2
electrons.
K-shell electrons are more tightly bound than the L-shell electrons
The K-shell has 1 energy level, the L-shell has 3 (L
1
, L
2
, L
3
)
and the M-shell has 5
2. X-rays
What is the relation between x-rays and matter?
The binding energy of inner electrons in the atom is of the same order of
magnitude as the energy of the X-ray photons.
X-rays can interact with the inner shell electrons.
Sub-shell K L
1
L
2
L
3

Binding energy (keV) 8.981 1.102 0.953 0.933

Energy levels in copper
Compare this with:
IR spectrometry: vibration rotation levels in molecules
UV-VIS spectrometry: binding energy levels
2. X-rays
Why x-rays interact with atoms?
Interaction of X-rays with matter
X-rays interact with atomic electrons in two fundamentally different ways
absorption of the photon
photoelectric absorption is the dominant interaction, causes the
generation of the characteristic X-rays in the sample.
scattering of the photon
responsible for most of the continuum observed in XRF spectra
(part of the exciting radiation is scattered by the sample and
enters the detector system)
Types of interaction
2. X-rays
How do x-rays interact with matter?
Photoelectric absorption
a photon is completely absorbed by
the atom, an (inner shell) electron is
ejected.
Part of the photon energy is used to
overcome the binding energy of the
electron, the rest is transferred to the
electron in the form of kinetic energy
2. X-rays
What happens during photoelectric absorption?
After the interaction, the atom
(actually ion) is in a highly excited
state. A vacancy has been created
in one of the inner shells.
The atom will almost immediately
return to a more stable electron
configuration emission of an Auger
electron or a characteristic X-ray
photon.
Photoelectric absorption can only occur if E
Photon
> E
ab
!!!
At high energy the probability of ejecting a electron is rather low
Photoelectric absorption cross section
Cu
2. X-rays
How big is the interaction probability?
At 8.98 keV there is an abrupt decrease in the cross section
X-rays with lower energy can only interact with the L- and M- electrons.
At E slightly greater than 8.98 keV the cross section is higher !!!
absorption
edges
Elastic and Inelastic Scattering
Scattering causes the photon to change direction.
Elastic or Rayleigh scattering
The energy of the photon is the same before and after scattering
Forms the basis of X-ray diffraction.
Inelastic or Compton scattering
The photon loses some of its energy
A photon having an initial energy E, after
undergoing inelastic scatter will deflect
over an angle with an energy E' given
by the Compton equation:
e-
K L M
>
Compton Scatter
Rayleigh Scatter
'
) cos 1 (
511
1 -
E
+
E
= E

E = 20 keV, = 90 E' = 19.25

2. X-rays
What happens during scattering?
X-ray attenuation
X-rays pass through matter photons will be lost
by photoelectric absorption
by scattering
) exp(
0
d I I =
is the density and is called the mass attenuation coefficient.
The total mass attenuation coefficient is the contribution from photo-
electric absorption, coherent and incoherent scattering
Inc Coh Photo
+ + =
Lambert-Beer law
I
I
0
d
2. X-rays
What is the consequence of all this?
After photoelectric absorption the atom is in a highly excited state.
The vacancy will be filled by an electron from a higher shell.
The energy difference between those two states, (vacancy in the K-shell
and vacancy in the L
3
-shell) can be emitted as an X-ray photon.
These X-rays are called "characteristic" because their energy is different
for each element, as every element has its own energy levels.
The emission is governed by quantum mechanical selection rules.
n > 0, l = 1, and j = 0 or 1.
Characteristic X-rays emission
2. X-rays
How do we get characteristic x-rays?
2. X-rays
Can an atom emit different x-ray lines?
Characteristic X-rays lines
K - alpha lines: L shell e-
transition to fill vacancy in K
shell. Most frequent
transition, hence most intense
peak.
K - beta lines: M shell e-
transitions to fill vacancy in K
shell.
L Shell
K Shell
L - alpha lines: M shell e-
transition to fill vacancy in L
shell.
L - beta lines: N shell e-
transition to fill vacancy in L
shell.
K alpha
K beta
M Shell
L alpha
N Shell
L beta
2. X-rays
What did we learned from this?
Summary
1. x-rays are electromagnetic radiation with an energy in the same
range as the binding energy or inner (K, L-shell) electrons
2. the main interaction is the photo-electric effect
3. the decay of the vacancy created the PE-effect causes the emission
of characteristic x-rays
4. there are K, L and M x-ray lines
XRF instruments
sample holder
x-ray source (excitation of the sample)
spectrometer (measures energy/wavelength and counts x-rays)
wavelength-dispersive spectrometers WD-XRF
energy-dispersive spectrometers ED-XRF
XRF Instrumentation
3. Instrumentation
What are the essential parts of an XRF?
X-ray tubes
The tungsten filament (the cathode) and anode are in an vacuum glass tube.
The anode: very pure metal (Cr, Mo, Rh, Ag, W)
The filament is heated by the current from a low voltage power supply
causing emission of electrons from the W-wire.
The negative high-voltage (e.g., -30 kV) applied to the filament,
accelerated the electrons to the anode at ground potential
The generated X-rays escape from the tube via a beryllium window.
3. Instrumentation
How does an x-ray tube works?
X-ray production
Due to the interaction of the electrons with the atoms of the anode
1) characteristic X-rays: emission of characteristic X-rays from the anode
2) continuous X-rays: deceleration of the electrons in collisions with the target atom
"Bremsstrahlung" (German, break-radiation)
spectrum from a Rh-anode X-ray tube operated at 45 kV
The shape depends on:
applied voltage
anode material
Be window thickness
Short wavelength limit
accelerating voltage V=45 kV
E
max
= 45 keV
or
min
= 12.4/V = 0.28
X-ray tube spectra
3. Instrumentation
How is the x-ray spectrum of an x-ray tube looking?
Radioactive sources
Radio-nuclides emitting X-rays or low energy gamma rays
transitions in the nucleus gamma rays:
electron capture emission of X-rays
Electron capture decay
55
Fe (26 p
+
and 29 n) captures an (K) orbital electron
p
+
+ e
-
n
resulting in
55
Mn (25 p
+
and 30 n ) and a vacancy in the K-shell
emission of Mn K-L
3,2
or Mn K-M
3,2
X-ray.
Activity
expressed in becquerels
(1 Bq = 1 disintegration per second = 2.7x10
-11
Ci).
typically 100 to 300 MBq (~3 to 10 mCi).
Half-life, t

After a time equal to t

, the intensity of the source is reduced to 50% of

its initial value
Usage
portable ED-XRF systems that can be operated in the field.
radio-isotope sources
3. Instrumentation
Can we use radio-nuclides as x-ray sources?
Some sources commonly used in radioisotope excited XRF
13.61,
17.22
U-L x-rays 60
238
Pu
13.95,
17.74
60
Np-L X-rays
g-ray
433
241
Am
22.10,
24.99
88
Ag-K X-rays
-ray
1.27
109
Cd
5.89, 6.49 Mn-K X-rays 2.7
55
Fe
Energy,
keV
Radiation Half-life,
T

(y)
Radioisotop
e
radio-isotope sources
3. Instrumentation
Which sources can we use?
Wavelength-dispersive spectrometers
Crystal spectrometer
based on the principle of Bragg diffraction.
) 2 1 ( sin 2 K , , = n n = d
the x-rays reflected from the second plane (b) travel
a distance xyz = 2dsin further
x-ray waves will out off phase after reflection (intensity 0)
except if the difference = an integer number of wavelengths
(constructive interferences) condition for Bragg diffraction:
3. Instrumentation
Who are x-rays reflected by a crystal?
Layout of an WD-spectrometer
Crystal and
plane
2d (nm) wave-length
range ()
Typical element
range
LiF (200)
Lithium
fluoride
0.402 3.88 - 0.52

K - Cd (K-lines)
Sn - U (L-lines)
PET (002)
Pentaerythritol
0.874

8.44 - 1.14 Al - Cl
3. Instrumentation
How does a WD spectrometer works?
x-ray detectors for WD spectrometers
Flow proportional counter
Scintillation counter
3. Instrumentation
How are the x-rays counted?
WD spectrum of a geological material between 0.69 and 0.98
3. Instrumentation
How do WD spectra look?
Measurement of WD spectra
Resolution very good little peak overlap
Measurement sequential takes much time
measure only at peaks and some background points
3. Instrumentation
What is de principle behind ED spectrometers?
Energy-dispersive spectrometers
The heart of an ED-spectrometer is a semi-conductor crystal (Si, Ge)
a high voltage is applied over the crystal (bias -600V)
and the crystal is cooled (e.g. at liquid nitrogen temperature)
When x-rays enter the crystal electron-hole pairs are formed
the number is proportional to the energy of the x-ray
because of the bias the electrons are swept out of the crystal
For each photon an electric
pulse is produced with an amplitude
proportional to the energy
Measuring the amplitude and
counting produces the ED-spectrum
3. Instrumentation
How does a the detector looks like?
Si(Li) crystal
-
+ +
+
+
+
+ +
+
+
-
- -
-
-
-
-
Be-window
7.5 m
X-ray photon
Preamp
-500 V
-196 C
Liquid Nitrogen cooled
Area: 30 - 100 mm
2
Thickness 3 - 5 mm
Resolution ~150 eV @ Mn Ka
3. Instrumentation
How is the detector cooled?
Detector and cryostat
2 4 6 8 10 12 14 16 18
1
10
100
1k
10k
Mo, scatter
Sr Rb
Ti,Ba
Zn
Al
Si
Ca
K
Fe
Energy (keV)
3. Instrumentation
Energy-dispersive spectrum
ED-spectrum of geological standard JG1
Si Pin-diode detectors
Area 5 - 10 mm
2
, Thickness ~0.3 mm
Resolution: ~250 eV @ Mn Ka
3. Instrumentation
Are there other types of semi-conductor detectors?
Si PIN diode detector
3. Instrumentation
What is best?
ED versus WD spectrometers
Wavelength dispersive spectrometers
very good resolution (10-20 eV) -> no peak overlap
sequential
complex mechanical design
simple electronics
Energy-dispersive spectrometers
lower resolution (150 200 eV) -> much peak overlap
simultaneous
simple mechanically
electronically complex
3. Instrumentation
What did we learned from this?
Summary
1. An XRF needs a x-ray source, a sample holder and a detector
2. Based on the detector we distinguish between wavelength and
energy dispersive spectrometers (WD-XRF and ED-XRF)
3. As x-ray sources we can x-ray tubes or radio-isotopes
4. WD spectrometers rely on Bragg reflection to disperse the x-rays
they have good resolution but are mechanically complex
5. ED spectrometers use a semi-conductor crystal to measure the
energy and count the x-rays. Their resolution is not so good but
they are small and simpler in use.
sophisticated mechanical design
rotation of the goniometer
selection crystals, detectors, collimators and filter
Sequential (or single channel) WD-XRF instruments
one goniometer.
goniometer moved to the correct 2 angle for each element
the intensity is measured for 1 to 100 s
entire measurement of a sample ~30 minutes
simultaneous (or multi-channel) instruments
a number of crystal-detector combinations at fixed 2
up to 30 channels.
multi-element analysis of a fixed set of elements in a few
seconds
ideally for process control, e.g., in the steel industry
WD-XRF Configurations
4. XRF configurations
What do we need to make a WD-XRF?
Combined sequential and fixed WD-XRF spectrometer
WD-XRF spectrometer
4. XRF configurations
How are the parts put together?
WD-XRF instruments
4. XRF configurations
How do they look in reality?
Philips instrument with automatic sample changer
ED-XRF configurations
4. XRF configurations
How can we make configurations with the ED detector?
x-ray
tube
collimator
filter
sample
detector
Direct tube excitation
Sample
Detector
X-ray tube
Secondary
target
Collimator
& filter
Secondary target
excitation
ED-XRF configurations
4. XRF configurations
Are there other configurations possible?
Radio-isotope
excitation
4. XRF configurations
Can it be even more crazy?
Micro-XRF
synchrotron
radiation
x-ray capillaries
Philips MiniPal
Rh x-ray tube
Si PIN Diode detector
Examples of ED-XRF instruments
4. XRF configurations
How do they look like?
Radioisotopes
Energy-dispersive detectors
Si(Li) Detector
Pin diode
Portable ED-XRF instruments
4. XRF configurations
Are there instruments we can use in the field?
What did we learned from this?
Summary
4. XRF configurations
1. WD instruments are complex, they operate many sequential
2. There are many ED-XRF configurations including portable and
laboratory made
i
i
w

I

XRF analysis
Intensity in cps of the Fe K-L
3,2
line
for an iron concentration of 1% in various matrices
20 79 22 108 1200 Int. Fe K-L
3,2
Pb Ni Cr Al C Matrix
5. XRF analysis
How do we obtain analytical information?
Wavelength (2 angle) / Energy (keV)
=> which element present
(qualitative analysis)
Intensity (number of x-ray per unit of time)
=> how much of each element
(quantitative analysis)
Relation depends on the sample composition (matrix)
I
i
, E
Fe K
I
o
, E
o

2
x
x + dx
d
X-ray source
Detector
Sample: 95 % Al,
5% Fe

1
Analysis of carbon in steel
237 3.46
262 3.80
204 2.87
274 3.89
243 3.45
209 2.93
158 2.32
C K X-ray
intensity in
counts/s
C
concentration
in wt%
straight line calibration:
Int C K (cps) = (-0.05 10) + (69.9 3.1) x Conc
150
200
250
300
2.00 2.50 3.00 3.50 4.00
Concentration C, Wt%
I
n
t
e
n
s
i
t
y

C

K
a
XRF calibration
5. XRF analysis
Are there simple cases?
XRF fundamental parameter quantization
5. XRF analysis
Is there a general method?
Fundamental relation between x-ray intensity and concentration
relies on many physical constants and parameters
need sophisticated computer programs to solve (iteratively)
0 0 0 0 0
max
0
) , ( ) (
1
) ( ) ( dE E E A E fI
r
r
E W E G N
E
E
i K
K
K
i i i F i
K

|
|
.
|

\
|
+
(

|
|
.
|

\
|
+
=

sin
) (
sin
) (
sin
) (
sin
) (
exp 1
) , (
0
0
0
i
i
i
E E
X
E E
E E A
0 0 0 0 0
1
2
1 2 1
max
0
) ( ) , ( ) (
) sin(
) (
4
dE E I E E A E Q
E d
d d d I
E
E
i if
i
i
K

f
r
r
E Q
K
K
K
i if

1
) (
0

=
Example fundamental parameter quantization
5. XRF analysis
Can we obtain good results with this method?
Standardless quantitative analysis of NIST 1200 Cr-Co-Ni alloy
using Rh tube-excitation (Spectrace 5000 XRF) WinFund
Concentrations in Wt%
Elem-Line Calculated Certified Diff
Ti-Ka 0.11 0.03 -0.08
Cr-Ka 20.87 19.9 -0.97
Mn-Ka 1.67 1.34 -0.33
Fe-Ka 3.18 3.19 0.01
Co-Ka 42.12 42 -0.12
Ni-Ka 19.91 20 0.09
Nb-Ka 3.34 3.18 -0.16
Mo-Ka 4.55 4 -0.55
Ta-La 1.06 1.08 0.02
W -La 3.17 3.86 0.69
Spectrum evaluation in ED-XRF
5. XRF analysis
Are there other problems?
We need net x-ray without background and interference
Computer programs to evaluate the ED-XRF spectra
What did we learned from this?
Summary
5. XRF analysis
1. There exists matrix effects so that the relation between
concentration and intensity is not so simple
2. For a constant matrix we can use simple calibration
3. We can also use the fundamental parameter relation
4. We need to analyze the ED spectra because of the peak overlap