1

Lecture Date: February 4

th
, 2008
X-ray Spectrometry
Notes
- See Chapters 12 and 21 (mostly Chapter 12) of Skoog
- This lecture covers both atomic and molecular
applications of X-ray spectrometry
- X-ray diffraction is only briefly discussed here - it is
covered in its own lecture along with its applications to
crystallography and solid-state structural analysis
- Surface analysis and microscopy is also briefly discussed
in advance of its own lecture
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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)
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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

h
h
eV = = (where V
0
is the electron accelerating voltage)
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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
( ) = 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
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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.
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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
R. Jenkins, et al., Pure Appl. Chem., 63, 736-746 (1991).
X-ray Generation: Characteristic Radiation
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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
I. Szaloki, J. Osan, andR. E. VanGrieken, X-ray Spectrometry, Anal. Chem., 76, 3445-3470 (2004).
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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.
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Energy-Dispersi ve Anal yzers
- 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-Dispersi ve Anal yzers
- The Si(Li) detector:
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Energy-Dispersi ve Anal yzers: Typical Spectra
- An ED X-ray spectrum from a Si(Li) detector, for qualitative
analysis:
J. I. Goldstein, D. E. Newbury, P. Echlin, D. C. Joy, A.D. Romig, Jr., C. E. Lyman, C. Fiori, andE. Lifshin, Scanning
ElectronMicroscopyandX-Ray Microanalysis, 2ndEdition, PlenumPress, 1992.
Wavelength-Dispersi ve Anal yzers
- 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
sin 2d n =
d
n
2
sin

=
Reflection occurs when:
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Wavelength-Dispersi ve Anal yzers
- The Rowland design:
DiagramfromStrobel and Heineman, Chemical Instrumentation, A
Systematic Approach, Wiley, 1989.
Wavelength-Dispersi ve Anal yzers: Typical Spectra
WD offers much higher energy
resolution than ED, better sensitivity,
and better reproducibility (precision) for
quantitative analyses
FiguresfromMcSwiggenandAssociates,www.mcswiggen.com
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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
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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

K Auger
=1
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XRF: Typi cal 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
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Applications of XRF to Qualitati ve and
Quantitati ve Anal ysis
- 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 Technol ogy
- 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
TheInnov-X Systems Alpha Series, seehttp://www.innov-xsys.com
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Applications of Hand-Held XRF Technol ogy
- Rapid, non-invasive
XRF analysis of
wood waste found
in Hurricane
Katrina debris for
arsenic
B. Dubey, H. M. Solo-Gabriele,andT. G. Townsend, Quantitiesof Arsenic-TreatedWoodinDemolitionDebrisGeneratedbyHurricaneKatrina,
Environ. Sci. Technol.41(5) 15331536(2007).
- 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
J. I. Goldstein, D. E. Newbury, P. Echlin, D. C. Joy, A.D. Romig, Jr., C. E. Lyman, C. Fiori, andE. Lifshin, Scanning
ElectronMicroscopyandX-Ray Microanalysis, 2ndEdition, PlenumPress, 1992.
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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
- Will be discussed in the
Surface Analysis Lecture
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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
Diagramof PIXE Instrument fromwww.mrsec.harvard.edu (2006)
X-ray Emission: PIXE
- PIXE: J ust 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 imagesfromwww.ipp.phys.ethz.ch and www.tiara.taka.jaeri.go.jp (2006)
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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 fromwww.nasa.gov (2006)
X-ray Emission: APXS
- APXS spectra from Mars: easy detection from sodium to iron
Images fromwww.nasa.gov (2006)
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X-ray Absorpti on
- 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 #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 Absorpti on
- 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.
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X-ray Absorpti on 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 Absorpti on 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).
DiagramfromM. Newville, Fundamentals of XAFS, Universityof Chicago, 2003.
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EXAFS
SlidefromM. Newville, Fundamentalsof XAFS, Universityof Chicago, 2003.
EXAFS
SlidefromM. Newville, Fundamentalsof XAFS, Universityof Chicago, 2003.
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XANES
- XANES often empirically interpreted see new ref Rehr,
J . J ., Ankudinov, A. L., Progress in the theory and
interpretation of XANES Coordination Chemistry Reviews,
J an 2005
DiagramfromM. Newville, Fundamentals of XAFS, Universityof Chicago, 2003.
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.
DiagramfromCharlesEvansandAssociateswebsite(http://www.cea.com)
http://www.cea.com/cai/augtheo/caiatheo.htm
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Homework Problems
From Chapter 12 of Skoog et al.:
12-2
12-9
Further Reading
I. Szaloki, et al., X-ray Spectrometry, Anal. Chem., 2002,
74, 2895-2918.