Instrumentation for EDXRF

a comparison of features
Dr. Roman Padilla Alvarez
IAEA consultant

1/19/17

Outline

Excitation sources
Detectors
Signal processing
Geometric arrangement
Software for spectrum deconvolution

1/19/17

Hardware for excitation

Sources

Radioisotopes (, , x-rays)

X-Ray Tubes

Electrons (SEM)

Charged particles (accelerators)

Synchrotron radiation

1/19/17

Hardware for excitation

Sources

Radioisotopes (, , x-rays)

X-Ray Tubes

Electrons (SEM)

Charged particles (accelerators)

Synchrotron radiation

1/19/17

Radioisotopes

1/19/17

Radioisotopes

Isotope

55

Fe

244

Energy (keV)

5.9

Elements
(K-lines)
Elements
(L-lines)

Cm

Cd

Am

Co

109

241

57

14.3,
18.3

22.1,
88

59.5

122

Al V

Ti-Br

Fe-Mo

Ru-Er

Ba - U

Br-I

I- Pb

Yb-Pu

None

none

While isotopes have fallen out of favor they are still

useful for many gauging applications.

1/19/17

Radioisotopes: Advantages and limitations

Pros
o Compact, simple construction

Portability

Monochromatic excitation

Low cost

Cons
o Change in flux due to radioactive decay
o

Constant radiation exposure

Non-tunable energy

1/19/17

End Window X-Ray Tube

X-ray Tubes
o Voltage determines
which elements can be
excited.
o More power = larger
sensitivity
o Anode selection
determines optimal
source excitation
(application specific).

1/19/17

Side Window X-Ray Tube

Glass Envelope

Be Window
Target (Ti, Ag,
Rh, etc.)

HV Lead

Electron beam

Copper Anode
Filament

Silicone Insulation

1/19/17

Intensity

Production in an x-ray tube

Characteristic
Lines

Continuum
Distribution

E0
N ( E )E kiZ
E
E 1
E0
Energy

1/19/17

Tunable energy distribution

1/19/17

X-ray tubes: Advantages and limitations

Pros

o Different anode materials available

o Tunable energy by selecting HV
o Low power tubes can be even portable
o Not constant radiation exposure (on/off)
o Possibility to use modifyiing devices

Cons
o Require of power generator
o

For power 600 w cooling system is required

Limited life time (~ 3000 hrs)

1/19/17

Hardware for excitation

Modifiers

Energy selection:
o Filters

Monochromators

Secondary targets

Spatial:
o Collimators
o

x-ray optics devices

1/19/17

Hardware for excitation

Modifiers

Energy selection:
o Filters

Monochromators

Secondary targets

Spatial:
o Collimators
o

x-ray optics devices

1/19/17

Absorption filters

Titanium Filter transmission curve

%
T
R
A
N
S
M
I
T
T
E
D

Absorption
Edge

Low energy x-rays

are absorbed

Very high energy

x-rays are transmitted

X-rays above the

absorption edge energy are
absorbed

ENERGY

Ti

Cr

The transmission curve shows the parts of the source

spectrum are transmitted and those that are absorbed
1/19/17

Absorption filters

1/19/17

Absorption filters (Ag tube)

1/19/17

Hardware for excitation

Modifiers

Energy selection:
o Filters

Monochromators

Secondary targets

Spatial:
o Collimators
o

x-ray optics devices

1/19/17

Hardware for excitation: Monochromator

Energy selection based on Bragg diffraction

1/19/17

Hardware for excitation

Modifiers

Energy selection:
o Filters

Monochromators

Secondary targets

Spatial:
o Collimators
o

x-ray optics devices

1/19/17

Secondary targets

Improved Fluorescence and lower background

The characteristic fluorescence of the anode
source is used to excite the sample, with the
lowest possible background intensity.
It requires almost 100x the flux of filter methods
but gives superior results.

1/19/17

Secondary targets

1/19/17

Comparison ST vs Direct or filtered

1/19/17

Hardware for excitation

Modifiers

Energy selection:
o Filters

Monochromators

Secondary targets

Spatial:
o Collimators
o

x-ray optics devices

1/19/17

Policapillary lens

1/19/17

Policapillary lens vs Pinhole

Spot size ~ 15 - 20 m
Gain in intensity x 300

1/19/17

Detectors

Proportional Counters
Scintillation Detectors
Si(Li)
LEGe
PIN Diode
SDD
CCD cameras
CZT, other

Poor energy resolution

WDXRF

Improved energy resolution

EDXRF

1/19/17

Semiconductor detectors: Principle of work

1/19/17

Main features of detectors

Efficiency
o How many photons produce a signal

Energy resolution
o Capability to differentiate close by
amplitude (energy) signals

Charge collection time

o Time required to collect charge

1/19/17

Intrinsic Efficiency

T: Fraction that is transmitted through the entrance layers

D: Fraction that is detected in the sensitive volume

1/19/17

Efficiency for various semiconductor detectors

1/19/17

Energy resolution

1/19/17

Si(Li)

Energy resolution ~ 160 180 eV (Mn-K )

Charge collection ~ 10 s
Input capability ~ 105 photons/sec
1/19/17

PIN

Energy resolution ~ 180 190 eV (Mn-K)

Charge collection ~ 10 s
Input capability ~ 105 photons/sec
1/19/17

Silicon Drift (SDD)

Energy resolution ~ 140 160 eV (Mn-K)

Charge collection ~ 1 s
Input capability ~ 106 photons/sec
1/19/17

Analog signal processing

1/19/17

Analog signal processing

Total time for processing one pulse ~ 15-20 s

1/19/17

Digital signal processing (DSP)

Total time for processing one pulse ~ 15-20 ns

1/19/17

Geometry arrangement: Excitation and

detection angles

Maximize the detection of x-ray emission while minimizing

the detection of the primary radiation scattered at the
sample
Diff Coherent Scat sections (E0=17.443)

0.9

Si
Fe

0.8
0.7

Si
Fe
Zr

0.018
0.016

Zr

0.6

Diff Incoherent Scat sections (E0=17.443)

0.02

0.014
0.012

0.5

0.01

0.4

0.008

0.3

0.006

0.2

0.004

0.1

0.002

0
0

30

60

90 120 150 180 210 240 270 300 330 360

Scatter angle

0
0

30

60

90

120

150

180 210

240

270

300 330

360

Scatter angle

1/19/17

Geometry arrangement: Effective Solid angles

1/19/17

Modelling a XRF peak

Peak described by a Gaussian
n2

2 y i yi

Continuum

xi x p 2

y i b H exp

i n1

Peak position

2 2

Peak height

Peak width

10000

Spectrum yi
Fit y(i)

8000

Minimum:
No direct analytical solution
Search 2 for minimum

6000

4000

2000

0
280

300

320

340

360

380

Channel, i

1/19/17

The need for advanced peak model

Cu K Zn K
100k
Cu K
Zn K

10k
Fe K Ni
Cu esc K

1k

100
Pb L
10

1
200

300

400

500

600

700

1/19/17

Advanced models for spectrum deconvolution

P i, E jk G i, E jk f S S i, E jk fT T i, E jk
G i, E jk

E i E jk 2
Exp

2
2 S jk
2

Gain
S jk

Gaussian
Shelf
Tail

2.0

E i E jk
Gain
erfc
Step: S i, E jk

2 E jk
2

Intensity, arbitrary units

Gaussian:

1.5

1.0

0.5

0.0

2.0

3.0

4.0

5.0

6.0

Energy, keV

Tail: T i, E jk

E i E jk
E i E jk
Gain
1

exp

erfc

1
2
2

2 exp 2
2
1/19/17

7.0

8.0

Determination of step and tail parameters

10

10

10

10

R e sid u a ls

Intensity, # counts

Fit of pure metal foils spectra

Spectrum
Fit
Cont.
Step
Tail

10

11

12

10

11

12

6
4
2
0
-2
-4
-6

Energy, keV

1/19/17

Software for spectrum deconvolution

QXAS

WinQXAS

PyMCA

WinAxil

bAxil

Released by

IAEA

IAEA

ESRF

Canberra

BrightSpec

Availability

Free upon
request

Free upon
request

Free download $$$$

$$$$

Operating
Environment

DOS

Win 95

Win XP

Win 95-XP

Win 7-8

Multiple
ROIs(b)

No

Yes

No

No

No

Scatter
peaks fit

Basic models

Basic models

No

Advanced

Advanced

Spectrum
format
conversion

Old formats
*.asc (ASCII)
*.spe (QXAS)

*.asc (ASCII)
*.spe (QXAS)

Different
options

Multiple
Canberra &
Ortec, *.asc,
*.spe

*.asc, *.spe,
*.spc, *.txt,
*.csv, *.mps,
*.xml, *axml

Batch run

Yes

No

Yes

Yes

Yes

Multiple

Elemental
sensitivity

Fund. Par.

Elemental
sensitivity
Fund. Par.

No

Quantitative
tools

(a)

Notes: (a) Possibility of running on DOS Box for Windows

(b) Capable of selecting multiple Region of Interest for fitting

1/19/17

AXIL-DOS (IAEA, free)

1/19/17

Win QXAS (IAEA, free)

1/19/17

WinAxil (Canberra)

1/19/17

bAxil (BrightSpec)

1/19/17

 Gracias por su atencin !

1/19/17