SKA6014

ADVANCED ANALYTICAL CHEMISTRY

TOPIC 6
X-ray Spectrometry

Azlan Kamari, PhD
Department of Chemistry
Faculty of Science and Mathematics
Universiti Pendidikan Sultan Idris
Outline
X-ray absorption/fluorescence processes
Auger electron emission
Photoelectron emission

Excitation of X-rays
X-ray fluorescence, X-ray emission

X-ray Detection and Spectrometer Design
Energy-dispersive (ED) spectrometers
Wavelength-dispersive (WD) spectrometers

Methods and Applications
Topics mentioned here but discussed in detail during the Surface
Analysis and Microscopy Lecture:
Scanning electron microscopy an X-ray emission microprobe
Auger electron spectrometry (electron energy)
X-ray photoelectron spectrometry (again, electron energy)
The Electromagnetic Spectrum
X-rays
(Also gamma rays)
X-rays
What are X-rays? High energy photons.
Note: gamma rays are just high-energy X-rays

Advantages of X-ray spectrometric methods:
The X-ray spectrum is not very sensitive to molecular effects or
chemical state, or excitation conditions
This is because core electrons are usually involved in X-ray
transitions physical and chemical state have only minute
effects (I.e. gas vs solid, oxide vs. element).
Atomization is not necessary for elemental analysis
Precision and accuracy are good, spectra are simple
Surface-sensitive (penetration of 100 um at most)

Disadvantages of X-ray methods:
Surface-sensitive, if you want bulk analysis (often not a problem)
Modest limits of detection, compared to other elemental methods
(e.g. AA, ICP-OES, ICP-MS)
X-ray Production
X-ray are commonly
produced by bombarding a
target with electrons

The target emits a
spectrum with two
components:
Characteristic radiation
Continuous radiation
(also called white
radiation,
Bremsstrahlung
(braking radiation)

The Duane-Hunt limit
explains the cutoff of the
continuous radiation:
max
min
0
c
v

h
h
eV = =
(where V
0
is the electron accelerating voltage)
X-ray Generation: Characteristic Radiation
The characteristics lines in X-ray spectra
result from electronic transitions between
inner atomic orbitals.

The X-ray spectra for most heavy
elements are much simpler than the
UV/Vis spectra observed in ICP-OES, for
example. (Only a few lines!!!)

Big difference between X-ray and UV-Vis:
The radiation is ionizing, and doesnt just
excite electrons to higher levels.

Moseleys law: Predicts the basic
relationship of atom number and the
frequency of the characteristic lines.
( ) o v = Z K
where Z is the atomic number, and K and o are
constants that vary with the spectral series.
X-ray Processes: when an X-ray strikes an atom
X-ray Generation: Characteristic Radiation
X-ray transitions:
(Here denoted using
the Siegbahn
notation)

Remember the
quantum numbers:
n principal quantum
number
l angular
momentum quantum
number
s spin quantum
number (o
1
and o
2

have s = -1/2 and s =
+1/2)
j inner quantum
number, from
coupling of l and s
X-ray Generation: Characteristic Radiation
X-ray transitions,
for gold (Z=79),
using both optical
and X-ray
(Siegbahn)
notation.
X-ray Generation: Nomenclature
Example notations for Copper (K series) in different notations
Transition Siegbahn IUPAC
2p
3/2
1s Ko
1
KL3
2p
1/2
1s Ko
2
KL2
3p
3/2
1s K|
1
KM3
3p
1/2
1s K|
3

KM2
X-ray Generation: Characteristic Radiation
X-ray Generation: X-ray Tubes
X-ray tubes: fire electrons at targets that are selected for their x-
ray emission properties as well as their robustness, heat
conductivity, etc
(Note modern tubes are more efficient, no water cooling needed)
X-ray Generation: The Future
Goals
Short pulsed sources (femtoseconds)
Brilliant sources
Coherent
Small beam sizes

One way of getting there capillary optics (polycapillary
lenses)
Achieve a higher spectral efficiency and small spot size for
a given X-ray beam
Best as of 2004 19 keV focussed onto a 20-30 um spot
Design of X-ray Instrumentation
Two major types:
Wavelength dispersive spectrometers
Analogous to dispersive spectrometers encountered in
IR and UV-Vis spectroscopy
Radiation
Source
Sample
Wavelength
Selector
Detector
Energy dispersive spectrometers
No real analogy in dispersive spectrometry
Detects portions of a spectrum directly through its energy
Radiation
Source
Sample Detector
Design of X-ray Instrumentation
Most substances have refractive indices of unity (1) at X-
ray frequencies.
The reason X-radiation is so high-frequency that there is
no time for the electronic polarization needed to cause a
refractive index.

Therefore, mirrors and lenses for X-rays cannot be made
(in general), and other ways to control X-rays must be
found

X-rays can be diffracted by crystals.
Compare this to the rulings and gratings used in optical
spectroscopy the wavelength of X-rays is so short, that
only molecular diffraction gratings (crystals) can be used.
Energy-Dispersive Analyzers
Energy-dispersive (ED) analyzers are heavily used in:
X-ray fluorescence (XRF), especially portable or small-footprint
Electron microprobe (SEM)

The spectrometer is just a Si(Li) detector.
Si(Li) detectors are made of silicon doped with Li, usually cooled
using LN
2
or a refrigeration system
Usually called lithium-drifted silicon, also drifted germanium.
The detector is polarized with a high voltage

When x-ray photons hit the detector, electron-hole pairs
are created that drift through the potential, creating a
pulse thats magnitude is directly proportional to the x-
ray energy
Energy-Dispersive Analyzers
The Si(Li) detector:
Energy-Dispersive Analyzers: Typical Spectra
An ED X-ray spectrum from a Si(Li) detector, for
qualitative analysis:
Wavelength-Dispersive Analyzers
General layout of a WD X-ray monochromator and
detector:
Sample
(source of X-rays)
Wavelength-dispersing
crystal
Detector
(pulse height
detector)
u
u
Total = 2u
u sin 2d n =
d
n
2
sin

u =
Reflection occurs when:
Wavelength-Dispersive Analyzers
The Rowland design:
Wavelength-Dispersive Analyzers: Typical Spectra
WD offers much higher energy
resolution than ED, better sensitivity,
and better reproducibility (precision) for
quantitative analyses
Figures from McSwiggen and Associates, www.mcswiggen.com
Comparison of WD and ED X-ray Detectors
Most important advantages of WD: Higher resolution, sensitivity
Most important advantages of ED: Cheaper, faster (except for
multichannel WD)
Other differences (more detailed comparison):
The future CdTe and CdZnTe materials as ED detectors
Energy-Dispersive Wavelength-Dispersive
Fast qualitative analysis Slow qualitative analysis
Non-focusing spectrometer Focusing spectrometer
Analyzes all elements at once Analyzes one/few element(s) at a time

Low count rates (~2000 counts/sec) High count rates (~50000 counts/sec)

Poor resolution (140-150 eV/channel) Good resolution (5 eV/channel)
Limited detection limits (1% w/w) Good detection limits (0.01% w/w)
Adequate quantitative analysis Excellent quantitative analysis (0.03%)
Poor light element detection (typically down
to boron with windowless designs)
Excellent light element detection, including
quantitative analysis down to beryllium
Higher background (lowers S/N) Lower background (increases S/N)

Less expensive (simpler) More expensive (complex)

X-ray Fluorescence (XRF) Spectrometry
Review of the principles:
if an X-ray photon (the primary X-ray) is absorbed by
an atom, and it has enough energy, it can eject an
electron, leaving a vacancy
A higher energy electron will drop down to replace it,
emitting a secondary X-ray
The energy of the secondary X-ray (if it can be
detected) is the difference of the binding energy of
the two shells!!!
XRF is a similar process to the photoelectric effect
where an x-ray is absorbed and transfers all of its
energy to an electron
Both ED and WD spectrometers are widely available
X-ray Fluorescence
X-ray Fluorescence (XRF)
The XRF yield is
actually influenced
by the degree of
Auger electron
formation
Auger electrons
predominate at
lower Z
XRF can be produced by:
X-rays
Alpha particles (APXS)
Protons (PIXE)
Electron beams (SEM electron
microprobe)
created vacancies shell K of number
produced photons K of number
=
K
e
K Auger
e e =1
XRF: Typical Spectra
An ED XRF spectrum of a calibration standard:
Advantages and Disadvantages of XRF
Advantages:
Can be applied in-situ and
nondestructively to analytes with
little or no sample preparation
Speed very fast
Good accuracy and precision

Disadvantages:
Not as sensitive as UV/Vis
methods for elemental analysis
(only gets down to ppm level in
some cases)
Auger process reduces sensitivity
for lighter elements (Z < 23)
Windows and other spectrometer
components can limit elements to
those with atomic numbers
greater than 5-6 (i.e. carbon)
Philips PW2400 WDS
Applications of XRF to Qualitative and
Quantitative Analysis
Matrix Effects
Fluorescent X-rays can be produced by both the analyte
and the matrix
Electronic materials measurement of defects (elemental
impurities) in silicon
Machinery analysis of metal composition, effects of
machining, defects and abnormalities
Ceramics elemental composition and impurities
Biological specimens and foods
Petrochemicals analysis of liquids, catalysts, etc
Example: Calcium quantitative analysis in calcium carbonate
antacid tablets
Entire tablets can be analyzed in situ
Hand-Held XRF Technology
Miniaturized XRF technology
applications are growing:
Mining
Geology
Environmental analysis
Alloy analysis

Utilize lightweight x-ray
tubes and Si PiN diode
detector
No radioactive isotopes
http://www.spectroscopymag.com/spectroscopy/article/articleDetail.jsp?id=406625
The Innov-X Systems Alpha Series, see http://www.innov-xsys.com
Applications of Hand-Held XRF Technology
Rapid, non-
invasive XRF
analysis of wood
waste found in
Hurricane Katrina
debris for arsenic
Wood contains chromated copper
arsenate (CCA, now banned),
which was used to pressure-treat
lumber
Detection limit for As in low-density
samples is 10-100 ppm
Using Ko and K| lines at 10.54 and
11.73 keV
Scanning Electron Microscopy and X-ray
Microanalysis
A scanning electron
microscope is a popular
excitation source for X-ray
emission
Electrons (5 keV 30 keV) hit
a sample.
They penetrate about 1 um
They knock loose K and L shell
electrons

X-rays are emitted as higher
energy electrons drop down
to fill the hole

Electron-Induced X-ray Emission
X-ray Emission in Electron Microscopy
X-ray Emission is just one of a
multitude of processes that can
occur when electrons hit a
target

In an SEM/TEM/STEM, the
following are possible:
X-ray emission spectrometry
with mapping
Formation of images from
backscattered electrons
Diffractometric analysis

X-ray Emission: PIXE
PIXE: particle (proton) induced x-
ray emission
Diagram is from the PIXE system at
Harvard: requires a particle
accelerator (5-10 meters long)
PIXE is heavily used in art
conservation and archaeology
Diagram of PIXE Instrument from www.mrsec.harvard.edu (2006)
X-ray Emission: PIXE
PIXE: Just like electron-
induced x-ray emission, only
more efficient
Less damaging to the sample but
more sensitive
Less charging than electrons
Less lateral deflection (protons
are not multiply scattered like e
-
)
PIXE images from www.ipp.phys.ethz.ch and www.tiara.taka.jaeri.go.jp (2006)
X-ray Emission: APXS
APXS: alpha particle x-ray
spectrometry
Alpha particles better for exciting
light elements:
Na, Mg, Al, Si
X-rays better in exciting heavier
elements
Fe, Co, Ni
Relative effectiveness crosses
over at chromium
APXS a compact ED
spectrometer for light-medium
elements with a radioactive
curium-244 source
Images from www.nasa.gov (2006)
X-ray Emission: APXS
APXS spectra from Mars: easy detection from sodium to iron
Images from www.nasa.gov (2006)
X-ray Absorption
X-ray absorption is used for
totally different applications
that X-ray fluorescence and
emission.

Beer-Lambert law:
x
P
P
=
0
ln
x
P
0
P

x
P
P
M
=
0
ln
where is the linear absorption coefficient
(depends on the element and no of atoms):
where
M
is the mass absorption coefficient, which is
independent of the elements state and is the density
3
4
AE
Z
~
(E is the energy of the x-rays, A is the atomic mass
and Z is the atomic number). Also:
X-ray Absorption
Why do X-ray and atomic/molecular UV-Vis absorption
spectra look so different, with all that the two techniques
have in common?
Atomic absorption/UV-Vis spectra have peaks
X-ray absorption spectra have edges

Answer: the ionization!
Optical AA has a peak with a narrow bandwidth because an outer
shell electron is excited to a higher energy level a discrete
quantum process

X-ray absorption is caused by photoelectron ionization not as
discrete of a process since energy in excess of that required for
ionization appears as kinetic energy of the photoelectron.
X-ray Absorption Fine Structure (XAFS)
X-ray absorption fine structure (XAFS) refers to the details of how x-
rays are absorbed by an atom at energies near and above the core-
level binding energies of that atom.

Specifically, XAFS is the modulation of an atoms x-ray absorption
probability due to the chemical and physical state of the atom.

XAFS spectra are sensitive to the oxidation state, coordination
chemistry, and the distances, coordination number and species of the
atoms immediately surrounding the atom of interest.

XAFS needs an intense, energy-tunable source of X-rays (a
synchrotron).
X-ray Absorption Fine Structure (XAFS)
Two regions of the XAFS
spectrum:
EXAFS (extended x-ray
absorption fine
structure): Sensitive to
distances, coordination
number, and identity of
surrounding atoms

XANES (X-ray
absorption near edge
spectroscopy):
Sensitive to oxidation
state and coordination
(e.g. tetrahedral vs.
octahedral coordination
of an atom).
EXAFS
EXAFS
XANES
XANES often empirically interpreted
X-ray Photoelectron Spectroscopy and Related
Techniques
Scanning Auger, XPS,
UPS, ECSA, and
more

All are surface analysis
methods and will be
discussed during the
Microscopy and
Surface Analysis
lecture.
Diagram from Charles Evans and Associates website (http://www.cea.com)
http://www.cea.com/cai/augtheo/caiatheo.htm