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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
(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