EDS

What is EDS?
Energy Dispersive X-Ray Spectroscopy (EDS or EDX) is a chemical microanalysis
technique used in conjunction with scanning electron microscopy (SEM). The EDS
technique detects x-rays emitted from the sample during bombardment by an electron
beam to characterize the elemental composition of the analyzed volume.
Working Principle of EDS?
When the sample is bombarded by the SEM's electron beam, electrons are ejected from
the atoms comprising the sample's surface. The resulting electron vacancies are filled
by electrons from a higher state, and an x-ray is emitted to balance the energy difference
between the two electrons' states. The x-ray energy is characteristic of the element from
which it was emitted.
The EDS x-ray detector measures the relative abundance of emitted x-rays versus their
energy. The detector is typically a lithium-drifted silicon, solid-state device. When an
incident x-ray strikes the detector, it creates a charge pulse that is proportional to the
energy of the x-ray. The charge pulse is converted to a voltage pulse (which remains
proportional to the x-ray energy) by a charge-sensitive preamplifier. The signal is then
sent to a multichannel analyzer where the pulses are sorted by voltage. The energy, as
determined from the voltage measurement, for each incident x-ray is sent to a computer
for display and further data evaluation. The spectrum of x-ray energy versus counts is
evaluated to determine the elemental composition of the sampled volume
Usage areas of EDS:

Materials evaluation and identification

Contaminants
Elemental diffusion profiles
Glassivation phosphorus content
Multiple spot analysis of areas from 1 micron to 10 cm in diameter

Failure analysis
Contamination identification
Unknowns identification
Stringer location and identification

Quality control screening

Material verification
Plating specification and certification
Advantages:

User can quickly collect a full spectrum with the push of a button.
EDS is quicker in analyzing .
EDS system is inexpensive.

Disadvantages:

Low Resolution
On EDS the broad X-ray lines appear to be a single peak, which makes it
difficult to analyze individual X-ray lines.
The count rate is fewer as compared to WDS.

WDS
What is WDS?
A wavelength-dispersive spectrometer (WDS or EDS) uses the characteristic X-rays
generated by individual elements to enable quantitative analyses (down to trace element
levels) to be measured at spot sizes as small as a few micrometers. WDS can also be
used to create element X-ray compositional maps over a broader area by means of
rastering the beam. Together, these capabilities provide fundamental quantitative
compositional information for a wide variety of solid materials.
Working Principle of WDS?
The WDX operates in much the same way as EDX. Unlike the related technique of
Energy dispersive X-ray spectroscopy (EDX), WDX reads or counts only the x-rays of
a single wavelength, not producing a broad spectrum of wavelengths or energies.
Measurement of an element's abundance requires exciting an atom to produce X-rays,
focusing the X-rays through a crystal spectrometer to a detector, converting the X-rays
to photoelectrons, the crystal structure of sample diffracts the photons in principles of
Bragg's law. Which in turn generates an electrical signal whose magnitude is
proportional to the abundance of the element! This multi-step process involves many
potential breakdowns, but works reliably well to allow for routine analysis.
Usage areas of WDS:
Identification of spectrally overlapped elements
S in the presence of Pbor Mo
W or Ta in Si, or N in Ti

Detection of low concentration species (10-100 ppm)

P or S in metals
Contaminants in precious metal catalysts
Trace heavy metal contamination
Performance-degrading impurities in high temperature solder alloys

Analysis of low atomic number elements

Composition of advanced ceramics and composites
B in BPSG films (sensitivity to 2000 ppm)
Oxidation and corrosion of metals
Characterization of biomedical and organically modified materials

Advantages:

Higher Resolution
When compared to EDS, WDS exhibits superior peak resolution of elements
and sensitivity of trace elements
WDS system will have a count rate about 10x that of an EDS system

Disadvantages:

Because WDS cannot determine elements below atomic number 5 (boron),

several geologically important elements cannot be measured with WDS (e.g.,
H, Li, and Be).

The multiple masses of an element (i.e. isotopes) cannot be determined by

WDS.

WDS analysis is slightly time consuming.

EDS and WDS Comparison:

EDS

WDS

Spectral
resolution

Higher (160 eV and less)

Lower (2-10 eV)

Light
elements?

With windowless
window detector

Detection
Limits

~1000-5000 ppm

or thin With
synthetic
("crystals")

diffractors

<100-500 ppm

Specifications Cheaper, quicker but some More expensive, but with much
elements are too close better resolution giving lower
together to resolve (eg S Ka, detection limits.
Mo La, Pb Ma)
Overlapping
of Peaks

Yes

No

Auger Electron Spectroscopy

What is Auger Electron Spectroscopy?
Auger Electron Spectroscopy (AES) provides information about the chemical
composition of the outermost material comprising a solid surface or interface. The
principal advantages of AES over other surface analysis methods are excellent spatial
resolution (< 1 m), surface sensitivity (~20 ), and detection of light elements.
Detection limits for most elements range from about 0.01 to 0.1% (atomic).
Working Principle AES?
AES uses a primary electron beam to excite the sample surface. When an inner-shell
electron is ejected from a sample atom by the interaction with a primary electron, an
electron from an outer shell fills the vacancy. To compensate for the energy change
from this transition, an Auger electron or an x-ray is emitted. For light elements, the
probability is greatest for the emission of an Auger electron, which accounts for the
light-element sensitivity for this technique.
The energy of the emitted Auger electron is characteristic of the element from which
was emitted. Detection and energy analysis of the emitted Auger electrons produces a
spectrum of Auger electron energy versus the relative abundance of electrons. Peaks in
the spectrum identify the elemental composition of the sample surface. In some cases,
the chemical state of the surface atoms can also be determined from energy shifts and
peak shapes.
Applications:
Auger electron spectroscopy is a very powerful surface analytical technique that has
found applications in many fields of solid-state physics and chemistry.

AES is used to monitor the elemental composition of surfaces during physical

property measurements.
Several phenomena such as adsorption desorption, surface segregation from the
bulk, measurement of diffusion coefficients, and catalytic activity of surfaces
have been investigated using AES.
It has also been used to study the surface compositional changes in alloys during
ion sputtering. Chemical properties such as corrosion, stress corrosion,
oxidation and catalytic activity and mechanical properties such as fatigue, wear,
adhesion, resistance to deformation processes, and surface cracking depend on
surface properties.
Similarly, grain boundary chemistry Influences mechanical properties such as
low- and high-temperature ductility and fatigue, chemical properties such as
inter-granular corrosion and stress corrosion, and electrical properties.
AES has been used to relate surface and grain boundary chemistry to properties
of materials. AES has proved to be extremely valuable compared to most other
techniques, which are limited by either large sampling depth or poor sensitivity.

Advantages:

Spatial resolution is high.

Analysis is relatively rapid.
Surface or subsurface analysis can be performed.
It is sensitive to light elements (except H and He).
It provides reliable semi quantitative analysis.
Chemical information is available in some cases.

Disadvantages:

Insulators are difficult to study due to surface charging.

Surface may be damaged by the incident electron beam.
Precise quantitative analysis may require extensive work.
Sensitivity is modest (0.1 to 1 atom %).
Depth profiling by ion sputtering or sectioning is destructive.

XPS
What s XPS?
X-Ray Photoelectron Spectroscopy (XPS), also known as Electron Spectroscopy for
Chemical Analysis (ESCA), is an analysis technique used to obtain chemical
information about the surfaces of solid materials. Both composition and the chemical
state of surface constituents can be determined by XPS. Insulators and conductors can
easily be analyzed in surface areas from a few microns to a few millimeters across.
Working Principle of XPS?
The sample is placed in an ultrahigh vacuum environment and exposed to a low-energy,
monochromatic x-ray source. The incident x-rays cause the ejection of core-level
electrons from sample atoms. The energy of a photoemitted core electron is a function
of its binding energy and is characteristic of the element from which it was emitted.
Energy analysis of the emitted photoelectrons is the primary data used for XPS. When
the core electron is ejected by the incident x-ray, an outer electron fills the core hole.
The energy of this transition is balanced by the emission of an Auger electron or a
characteristic x-ray. Analysis of Auger electrons can be used in XPS, in addition to
emitted photoelectrons.
The photoelectrons and Auger electrons emitted from the sample are detected by an
electron energy analyzer, and their energy is determined as a function of their velocity
entering the detector. By counting the number of photoelectrons and Auger electrons
as a function of their energy, a spectrum representing the surface composition is
obtained. The energy corresponding to each peak is characteristic of an element present
in the sampled volume. The area under a peak in the spectrum is a measure of the
relative amount of the element represented by that peak. The peak shape and precise
position indicates the chemical state for the element.

Applications:

Surface analysis of organic and inorganic materials

Determining composition and chemical state information from surfaces
Depth profiling for thin film composition
Thin film oxide thickness measurements

Advantages:

XPS is good for identifying all but two elements.

Identifying the chemical state on surfaces, and is good with quantitative
analysis.
XPS is capable of detecting the difference in chemical state between samples.
XPS is also able to differentiate between oxidations states of molecules.

Disadvantages:

The smallest analytical area XPS can measure is ~10 um.

Samples for XPS must be compatible with the ultra high vacuum environment.
XPS is limited to measurements of elements having atomic numbers of 3 or
greater, making it unable to detect hydrogen or helium.
XPS spectra also take a long time to obtain. The use of a monochromator can
also reduce the time per experiment.

References:
http://www.mee-inc.com/hamm/energy-dispersive-x-ray-spectroscopyeds/
http://www.mcswiggen.com/TechNotes/WDSvsEDS.htm
https://www.oxford-instruments.com/products/microanalysis/wavelength-dispersivesystems-wds
https://www.phi.com/surface-analysis-techniques/aes.html
http://www.mecheng.iisc.ernet.in/~bobji/mspc/assign/AES.htm
https://www.phi.com/surface-analysis-techniques/xps-esca.html
http://www.kratos.com/applications/techniques/x-ray-photoelectron-spectroscopy
http://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Spectroscopy/P
hotoelectron_Spectroscopy/Photoelectron_Spectroscopy%3A_Application