Overview

 Introduction to X-rays
 Generation of X-rays
Session 6  Instrument components
 Methods and Applications
 X-ray fluorescence (XRF)
X-ray spectroscopic methods  PIXE: Particle-induced X-ray emission
X-ray absorption: XANES and EXAFS
(Skoog Chapter 12) 
 XPS/ESCA: X-ray photon spectroscopy/ Electron
Spectroscopy for Chemical Analysis (will be covered
in CH921)
 Other methods employing X-rays (not covered)

Electromagnetic radiation Absorption of X-rays

Spectroscopy = interactions between light & matter.
 When X-rays pass through matter, I0 is decreased
Generally associated with electronic excitation
due to absorption and scattering
E = h = hc/  Beer’s law also applies to X-rays

= frequency;  = wavelength X-ray absorption: I0 It << I0

 ln (I0 / I) = x
 ln (I0 / I) = Mx absorption,
x : sample thickness scattering
I0 & I : powers of incident & transmitted
 : linear absorption coefficient
 : density of sample
M (mass absorption coefficient,
independent of physical / chemical
state of element, units cm2/g)

X-rays: 10-5-100 Å (10-6-10 nm); conventionally 0.1-25 Å ■ Ability of each element to

Common energy unit for characterising X-rays: eV (electronVolt): absorb (M) increases with
1 kcal = 0.04336 eV 1 eV = 23.0627 kcal atomic number (Z):
X-rays: 400-40000 eV
 Absorption of X-rays Energies required for various
 Difference between the absorption of X-rays and lower excitation processes
energy radiation:
 X-rays have higher energy: does not only promote  Generation of excited atoms (not ions):
elevation of valence electrons to excited state (see AAS), moderately high temperatures, as in flame
but promotes core electron into continuum (= removes atomic emission, are sufficient
electron from atom  “Ionising radiation”)
 Absorption occurs when
 Energy required for ionisation: Example
h of X-rays ≥ absorption edge energy (energy required sodium:
to remove e-)
 3s electron (valence electron): 5 eV : can be
etc.
achieved thermally (e.g. in ICP for MS)
3s, 3p, 3d
E (absorption edge energy) for
 2s electron (L edge): 63 eV
L edges inner electrons: can be
ionisation increases with atomic  1s electron (K edge): 1041 eV ejected by
2s, 2p (L shell)
number (increased positive charge - X-rays
on nucleus: stronger attractive - electron beam
force on electrons) K edge
- particle beam
1s (K shell)

The absorption process and what

happens next (X-Ray) Fluorescence
photon with lower
 Absorption process ejects inner
frequency than photon 1: shell electron: excited ion
X-ray fluorescence with a “hole” in an inner shell
 One of 2 processes can follow:
•Emission of light from an excited state, but
2A
 2A: X-ray fluorescence energy is lower than that absorbed
 Electron with higher energy •Energy difference between absorbed and
“drops” into this “hole”
 The energy lost by this electron emitted radiation is lost radiationless (e.g. as
is emitted as radiation with a kinetic energy of ejected electron (in X-ray
1 defined wavelength fluorescence) or vibrations and rotations (in
 Emitted energy lower than that
absorbed molecular fluorescence)
 2B: Auger electron ejection
photon 1 2B  The excited atom looses energy
by ejecting a further electron
from an outer shell
electron:XPS Auger
electron  All 4 processes are used
analytically
 Generation of X-rays: Sources

 Bombardment of metal target with high-

Generation of X-rays and 
energy electron beam (X-ray tubes)
Exposure to primary X-ray beam, to create
Instrument components secondary X-ray fluorescence beam
 Radioactive source (decay yields X-ray
emission –  radiation)
 Particle beams (e.g. protons, positrons)
 Synchrotron radiation

X-ray tube X ray generation in X-ray tube

 Evacuated tube containing Tungsten filament (cathode)
Output consists of 2 kinds of radiation:
and metal target plated on a copper block (anode)
 End window or side window (made of Berryllium)  Characteristic lines: inverse
 Metal targets: W, Cr, Cu, Mo, Rh, Ag, Fe, Co photoeffect (electrons hit
material, photons are emitted)
 Electrons accelerated towards anode at potential of
~ 100 kV: Interaction with atoms generates X-rays  Bremsstrahlung: caused by
 X-rays pass through Beryllium window to sample slowing down (deceleration) of
the incident electrons via
side-window X-ray tube: interactions with atoms. Gives
continuum ("white") radiation

http://www.rstp.uwaterloo.ca/x_ray/equipment/xray_production.html
 Output from X-ray tube: Output from X-ray tube:
Bremsstrahlung Characteristic lines
 Characteristic lines superimposed on Bremsstrahlung
 Continuous  Caused by complete removal of an electron in inner shell
 Has well-defined short wavelength limit (0), and subsequent re-filling of hole by outer electrons (= X-
depends on accelerating voltage (V), but ray fluorescence). The transition process leads to the
emission of energy in the form of radiation
independent of target metal
 For elements with atomic number > 23: Simple X-ray
 Results from collisions between electrons in beam spectrum containing two sets of lines (K and L series)
and atoms in target  Minimum excitation Voltage for line spectrum increases
 Maximum energy given by Duane-Hunt Law: with atomic number
h0 = hc / 0 = Ve 3s, 3p, 3d orbitals

 V (accelerating voltage), e (charge of e-), h (Planck's

constant), c (speed of light), 2s,2p orbitals
0 (maximum frequency produced at V), 0 (low-
wavelength limit)
 0 = 12398 / V ( 0 in Å; voltage in Volt) 1s orbital

Characteristic lines:
Emission of X-rays: Nomenclature of lines
Moseley's Law
 Emission can be induced by bombardment  In 1914, H.G.S. Moseley discovered relationship between
with electrons, positrons, particles such as frequency of spectral line () and atomic number (Z)
protons
 …and X-rays ( X-ray fluorescence)  Linear relationship between
square root of frequency ()
and atomic number (Z):
Lines are distinguished by
etc.
the shell to which the  = c /  = a(Z-)2
electron transition occurs: 3s, 3p, 3d
e.g. K1 is the lowest energy  c (speed of light),
transition to the K shell 2s, 2p   (wavelength of x-ray),
 (frequency),
Kusually most intense  a (a constant),
lines 1s
 Z (atomic number),
 (constant based on series, K or L)
Typical Characteristic X-Ray Energies Sources ctd: Secondary Targets
generated by common X-ray tubes
Sample
Copper Target………………….....8.05 keV
Molybdenum Target…………..17.46 keV Detector
X-Ray Tube
Silver Target………………….....22.15 keV
Chromium Target……………..….5.39 keV Secondary Target

1. The x-ray tube excites the secondary target

2. The Secondary target fluoresces and excites the sample
3. The detector detects x-rays from the sample

• Gives cleaner spectra

• But: Requires more flux than other methods

Sources: Radioisotopes Sources: Synchrotron

 X-rays from radioactive decay
 Suitable for a range of elements, but not much
used

 Encapsulated and partially shielded

 Can produce continuum (see Bremsstrahlung)
and/or line (e.g. 2655Fe) spectra
 E.g. 55Fe: electron capture reaction with half-life of
2.6 years
 Mn K line at 5.9 eV (≙ 2.1 Å) good for fluorescence
and absorption methods
55
26 Fe + e- → 2555Mn* → 2555Mn + h

http://www.diamond.ac.uk/Home/About/Synchrotrons/Machine.html
Synchrotron: circular electron accelerator Source modifiers
Modify the shape or intensity of the source
spectrum or the beam shape:
Booster ring
 Source Filters
Electron gun
 Secondary Targets
 Polarizing Targets
Beamline with X-rays
 Collimators
Storage ring
 Focusing Optics

- Very fast electrons (close to speed of light: relativistic effects), pass through
magnetic fields:
- Give off very intense beams of x-rays, infrared and ultraviolet light

Filters Effect of source filters

 Can be between source and sample, or
between sample and detector X-ray tube with
 For restriction of wavelength range, tungsten target
e.g. for production of monochromatic beam
or for cutting off unwanted wavelengths
 For elimination of characteristic lines
for production of continuum spectrum
 For reducing background radiation
 For improving fluorescence yield Same target with Al
 Several target-filter combinations available filter: cuts off all low-
 Widely used in X-ray diffraction and energy photons incl.
fluorescence
characteristic W lines:
 Material in filters for X-ray diffraction
usually 1-2 less than emitter, eg Ni foil
Gives a source for clean
for Cu K measurements between
20 and 40 keV
wavelength
 Monochromator Collimators
 Dispersing element: crystal mounted on goniometer (rotating
table)
• Circular or slits
 Vary angle  between crystal face and incident beam • Restrict the size or shape of the source
 Diffracts X-rays according to Bragg's Law: n = 2d sin() beam for exciting small areas
 X-rays reflect from face of crystal only if sin() = n / 2d; at other  • Also used in monochromators
get destructive interference
 At any given , only a small range of wavelengths leave
monochromator

Collimator sizes range from

12 microns to several mm

lattice spacing (d)

x

Detectors for X-rays Diode-based detectors

 Working principle similar to diode-based
 Early X-ray: used photographic emulsion to
detectors used for optical and atomic
measure radiation
spectroscopies:
 Now detectors convert radiation into  Composed of a non-conducting or semi-
electrical signal conducting material between two electrodes at
 Several diode-based designs (Si(Li), PiN, SDD)) a defined potential
 Based on semiconducting solid materials  Radiation ionizes the detector material causing
 Proportional Counters it to become conductive, temporarily
 Based on ionisation of gas by incoming radiation  The newly "liberated" electrons are accelerated
toward the detector anode to produce an
 Electrons drift to anode to generate measurable current
output pulse
 Scintillation Detectors  The number of electron/hole pairs produced is
 Based on emission of light by material hit by X-rays proportional to the photon energy
 Can in principle be solid or liquid
 Scintillation Detector Exercise
Photo-multiplier tube
Scintillator Electronics

 What is the short wavelength limit of the continuum

produced by an X-ray tube having a silver target and
operated at 80 kV?

Window: Be or Al Count Rates: 10,000 to 1,000,000+ cps

Resolution: >1000 eV Connector

A Scintillator is a material that emits (low-energy) light when

absorbing X-ray radiation (e.g. sodium iodide)
Emitted light is detected in photomultiplier tube

Exercise Exercise

 The mass absorption coefficient for Ni, measured with
the Cu K line, is 49.2 cm2/g. Calculate the thickness of
the Ni foil that was found to transmit 36.1% of the
incident power of a beam of Cu K radiation. Assume
that the density of Ni is 8.9 g/cm3.
 The K lines for Ca, Zn, Zr, and Sn occur at 3.36, 1.44,
0.79, and 0.49 Å, respectively. Calculate an approximate
wavelength for the K lines of (a) V, (b) Ni, (c) Se, (d)
Br, (e) Cd, and (f) Sb.
 X-ray fluorescence (XRF)

Session 5 (2)
Methods and applications
XRF  One of most widely used of
PIXE all analytical methods:
XANES and EXAFS  Qualitative and quantitative
{XPS/ESCA} analysis of elements with
Other methods atomic number > 8
http://www.learnxrf.com/

XRF instruments Typical benchtop EDXRF

 Three types of XRF spectrometer:
instrument
 Non-dispersive (NDXRF)  Source: X-ray tube
 Energy dispersive spectrometers (EDX, EDS, or EDAX): OR radioactive
 Detector allows the determination of the energy of the photon material
when it is detected
 Simple design: no
 Simple design
 Lower power for source required monochromator
 Wavelength dispersive spectrometers (WDX or WDS):  Can use weaker
 Photons are separated by diffraction on single crystal before sources
detection
 Higher resolution, but more expensive sample  Higher resolution
 Generally, fluorescence is measured than wavelength
at a 90° angle: dispersive at  < 1 Å
 Lower resolution at
>1Å
detector source
 Energy Dispersive XRF:
working principle Wavelength-dispersive instrument
Sample
 Fluorescence generates a current in the detector
 The height of the pulse produced is proportional to the Detector
energy of the respective incoming X-ray

X-Ray Collimators
Source
Signal to Electronics
Element
A
Diff. crystal
Element
B
DETECTOR monochromator
 Source: X-ray tube
Element
C
Element  Requires monochromator with collimators and
D
diffraction device
 Single channel or multichannel

 Multichannel: up to 24 elements

XRF Applications XRF applications

 Qualitative analysis:
 E.g. Analysis of a bank note
 Wavelength dispersive
• Metals, alloys,  Restriction of hazardous
 Semi-quantitative: semiconductors substances:
 Measurement of peak height  Screening of toys and other
goods for toxic material
 Intensity  concentration  Packaging
 Px = PsWx
 Px = Intensity of peak
 Wx = weight fraction of element
 Ps = Intensity if Wx equals 1

Mining and exploration

• Environmental monitoring
• Soil, dust, air filters
Art and archeometry
Authentication

Dating

Conservation and
Restoration
 More areas of applications Quantitative analysis by XRF
 Ecology and environmental management: measurement  Beer's law also valid for fluorescence
of heavy metals in soils, sediments, water and aerosols  Precision equals or exceeds other methods
 Geology and mineralogy: qualitative and quantitative  Quantitative work possible if one can calibrate
analysis of soils, minerals, rocks etc.  Caveat re accuracy: Matrix effects are important -
 Metallurgy and chemical industry: quality control of raw analysed materials must be similar to available
materials, production processes and final products standards
 Paint industry: analysis of lead-based paints
 Jewelry: measurement of precious metals concentrations
 Fuel industry: monitoring the amount of contaminants in
fuels
 Food chemistry: determination of toxic metals in
foodstuffs
 Agriculture: trace metals analysis in soils and agricultural
products

Interferences in XRF: Spectral Matrix Interferences:

Absorption/Enhancement Effects
 Besides overlap between lines from different
elements:
 K & L Spectral Peaks (from source)  Absorption: Any element can absorb or scatter
 Bremsstrahlung (from source) the fluorescence of the element of interest
Rayleigh Scatter Peaks - “Elastic” Scatter

 X-rays from the X-ray tube or target strike atom without
 Enhancement: Characteristic X-rays of one
promoting fluorescence. element excite another element in the sample,
 Energy is not lost in collision (EI = EO) enhancing its signal
 Appear as source peaks in spectra
 Compton Scatter Peaks - “Inelastic” Scatter  Influence Coefficients, sometimes called alpha
X-rays from the X-ray tube or target strike atom without

promoting fluorescence corrections, are used to mathematically correct for
 Energy is lost in collision (EI > EO) Matrix Interferences
 Appear at slightly lower energy than Rayleigh Scatter

 Escape Peaks: X-rays affecting detector material

 Sum Peaks: 2 photons detected as 1 with double energy
 Elimination of “environmental Advantages/disadvantages XRF
interferences”: Air  Advantages
 Simple spectra
 Sample and hardware chambers of any XRF  Non-destructive (precious samples)
instrument may, in principle, be filled with air  Rapid, convenient, precise, accurate
 But: air absorbs low energy X-rays from light
elements (Z>20)  Disadvantages
 Two solutions:  Not as sensitive as other methods
 Difficult for light elements
 Vacuum – for use with solids or pressed pellets
 Expensive
 Helium – For use with liquids or powdered
materials

Frontiers: microfluorescence and imaging Particle-induced X-ray

X-ray microfluorescence: XRF emission (PIXE)
Spectrum from a single human ovarian adenocarcinoma cell
 Solid, liquid, thin film samples
 Excitation by proton beam
 Faster, and higher sensitivities than
other X-ray methods, especially for
lighter elements

X-ray
Microfluorescence
Imaging of Single
Cells (Zinc)
http://www.esrf.eu/UsersAndScience/Publications/Highlights/2000/microfo
cus/MIC8.html Example: Gutenberg Bible ink analysis
 Applicable to biological samples

X-Ray Absorption
Spectroscopy

Plant leaf XANES: X-ray absorption near

PIXE spectrum of rabbit kidney
(http://www.ehponline.org/realfiles/
members/1993/101-4/lowe-full.html)
M. Ali, Nuclear Instruments and
Methods in Physics Research edge spectroscopy
Section B: Beam Interactions with
Materials and Atoms EXAFS: Extended X-ray absorption
Volume 222, 2004, 567-576
fine structure spectroscopy

X-ray absorption spectrum: Example iodine

X-ray absorption spectra
L edges
 E.g. absorption spectrum for Pb ( ) Z= 82
 0.14 Å: photon energy = energy required to eject K e- (high energy) K edge
 Peaks at long : Removal
of e-s from L levels
(3 levels: 3 peaks)
 Absorption spectrum of
Ag ( ) Z=47 Energy (keV) Zoom-in: L-edges
 K edge for Ag at longer 
(lower energy),
lower atomic number
 K edge, L edge: refers to L edges
where the electron comes
from
 Can be measured in Energy
K edge
transmission or fluorescence. Fluorescence more sensitive Energy (keV)
 Absorption-edge fine structure Origin of fine-structure features
 XANES: X-ray absorption near-edge spectroscopy
 EXAFS: Extended X-ray absorption fine structure  Main process observed:
spectroscopy  Absorption of X-ray photon kicks
 Measured quantitiy: Absorption coefficient out core electrons
 Specific for single element  These photoelectrons have E =
 Often measured via fluorescence rather than directly h(photon) – Ebinding
detecting absorption
 Photoelectron is considered as wave
 This wave will be scattered by adjacent atoms
“Ripples” are due to  Primary wave and back-scattered waves will interfere
 Positive interference increases intensity of wave
interactions of atom  Negative interference decreases intensity of wave
under observation with  This manifests itself in changes in the absorption
neighbouring atoms spectrum at energies higher than the absorption edge

Interference of photoelectron wave How to get information out of an

scattered from neighbour atoms EXAFS spectrum: Fourier
Transformation
 Energy/wavenumber (e.g. cm-1) scale is
transformed into distance (e.g. cm or Å)

FT

 In this pattern, information on the neighbouring

atoms is contained
 Distance from central atom
 Type – how many electrons ?
 How many neighbours ? Compare with NMR: Time domain (s) is transformed into frequency domain (s-1)
 Techniques for (elemental) analysis of solid samples: Overview

Experimental set-up
 EXAFS requires high-intensity
monochromatic light source: Synchrotron

http://www-ssrl.slac.stanford.edu/mes/xafs/index.html

Useful Links
 http://www.spectroscopynow.com/

 http://jersey.uoregon.edu/vlab/elements/El
ements.html

 http://www.elementalanalysis.com/