Energy-dispersive X-ray spectroscopy

Energy-dispersive X-ray spectroscopy
Energy-dispersive X-ray spectroscopy
Energy-dispersive
X-ray
spectroscopy (EDS or EDX) is an
analytical technique used for the
elemental analysis or chemical
characterization of a sample. It is one
of the variants of X-ray fluorescence
spectroscopy which relies on the
investigation of a sample through
interactions between electromagnetic
radiation and matter, analyzing X-rays
emitted by the matter in response to
being hit with charged particles. Its
characterization capabilities are due in
[1]
EDS spectrum of the mineral crust of Rimicaris exoculata
large part to the fundamental principle
that each element has a unique atomic
structure allowing X-rays that are characteristic of an element's atomic structure to be identified uniquely from one
another.
To stimulate the emission of characteristic X-rays from a specimen, a high-energy beam of charged particles such as
electrons or protons (see PIXE), or a beam of X-rays, is focused into the sample being studied. At rest, an atom
within the sample contains ground state (or unexcited) electrons in discrete energy levels or electron shells bound to
the nucleus. The incident beam may excite an electron in an inner shell, ejecting it from the shell while creating an
electron hole where the electron was. An electron from an outer, higher-energy shell then fills the hole, and the
difference in energy between the higher-energy shell and the lower energy shell may be released in the form of an
X-ray. The number and energy of the X-rays emitted from a specimen can be measured by an energy-dispersive
spectrometer. As the energy of the X-rays are characteristic of the difference in energy between the two shells, and
of the atomic structure of the element from which they were emitted, this allows the elemental composition of the
specimen to be measured.
X-ray generation
The equipment measures the number of emitted X-rays. Higher accelerating voltages penetrate deeper into the
sample; the beam also penetrates deeper into lighter elements, which thus generate more counts.[2]
Equipment: the connection with SEM
There are four primary components of the EDS setup: the beam source; the X-ray detector; the pulse processor; and
the analyzer.
A number of free-standing EDS systems exist. However, EDS systems are most commonly found on scanning
electron microscopes (SEM-EDS) and electron microprobes. Scanning electron microscopes are equipped with a
cathode and magnetic lenses to create and focus a beam of electrons, and since the 1960s they have been equipped
with elemental analysis capabilities. A detector is used to convert X-ray energy into voltage signals; this information
is sent to a pulse processor, which measures the signals and passes them onto an analyzer for data display and
analysis.
1
Energy-dispersive X-ray spectroscopy
2
Technological variants
The excess energy of the electron that migrates to an inner shell to fill
the newly-created hole can do more than emit an X-ray. Often, instead
of X-ray emission, the excess energy is transferred to a third electron
from a further outer shell, prompting its ejection. This ejected species
is called an Auger electron, and the method for its analysis is known as
Auger electron spectroscopy (AES).
X-ray photoelectron spectroscopy (XPS) is another close relative of
EDS, utilizing ejected electrons in a manner similar to that of AES.
Information on the quantity and kinetic energy of ejected electrons is
used to determine the binding energy of these now-liberated electrons,
which is element-specific and allows chemical characterization of a sample.
Principle of EDS
EDS is often contrasted with its spectroscopic counterpart, WDS (wavelength dispersive X-ray spectroscopy). WDS
differs from EDS in that it uses the diffraction patterns created by light-matter interaction as its raw data. WDS has a
much finer spectral resolution than EDS. WDS also avoids the problems associated with artifacts in EDS (false
peaks, noise from the amplifiers and microphonics. In WDS, only one element can be analyzed at a time, while EDS
gathers a spectrum of all elements, within limits, of a sample.
Accuracy of EDS
Accuracy of EDS spectrum can be affected by many factors. Windows in front of the detector can absorb low-energy
X-rays (i.e. EDS detectors cannot detect elements with atomic number less than 4, that is H, He, and Li).[3]
Over-voltage settings in EDS alter the peak sizes – raising over-voltage on the SEM shifts the spectrum to the larger
energies, making higher-energy peaks larger and lower-energy peaks smaller. Also many elements will have
overlapping peaks (e.g., Ti Kβ and V Kα, Mn Kβ and Fe Kα).[4] The accuracy of the spectrum can also be affected by
the nature of the sample. X-rays can be generated by any atom in the sample that is sufficiently excited by the
incoming beam. These X-rays are emitted in any direction, and so they may not all escape the sample. The likelihood
of an X-ray escaping the specimen, and thus being available to detect and measure, depends on the energy of the
X-ray and the amount and density of material it has to pass through. This can result in reduced accuracy in
inhomogeneous and rough samples.
Emerging technology
There is a trend towards a newer EDS detector, called the silicon drift detector (SDD). The SDD consists of a
high-resistivity silicon chip where electrons are driven to a small collecting anode. The advantage lies in the
extremely low capacitance of this anode, thereby utilizing shorter processing times and allowing very high
throughput. Benefits of the SDD include:
1.
2.
3.
4.
5.
High count rates and processing,
Better resolution than traditional Si(Li) detectors at high count rates,
Lower dead time (time spent on processing X-ray event),
Faster analytical capabilities and more precise X-ray maps or particle data collected in seconds,
Ability to be stored and operated at relatively high temperatures, eliminating the need for liquid nitrogen cooling.
Because the capacitance of the SDD chip is independent of the active area of the detector, much larger SDD chips
can be utilized (40 mm2 or more). This allows for even higher count rate collection. Further benefits of large area
chips include:
1. Minimizing SEM beam current allowing for optimization of imaging under analytical conditions,
Energy-dispersive X-ray spectroscopy
2. Reduced sample damage and
3. Smaller beam interaction and improved spatial resolution for high speed maps.
In recent years, a different type of EDS detector, based upon a microcalorimeter, has become commercially
available. This new model allegedly has the simultaneous detection capabilities of EDS as well as the high spectral
resolution of WDS. The EDS microcalorimeter relies highly on two components: an absorber, and a thermistor. The
former absorbs X-rays emitted from the sample and converts this energy into heat; the latter measures the subsequent
change in temperature due to the influx of heat (in essence, a thermometer). The EDS microcalorimeter has suffered
from a number of drawbacks; including low count rates, poor collection efficiencies and small detector areas. The
count rate is hampered by its reliance on the time constant of the calorimeter’s electrical circuit. The collection
efficiency is a function of the absorber material and remains to be optimized. The detector area must be small in
order to keep the heat capacity as small as possible and maximize thermal sensitivity (resolution). Innovative
engineering solutions are necessary for further improvement of spectroscopic microanalysis.
References
[1] Corbari, L et al. (2008). "Iron oxide deposits associated with the ectosymbiotic bacteria in the hydrothermal vent shrimp Rimicaris exoculata"
(http:/ / www. ifremer. fr/ docelec/ doc/ 2008/ publication-4702. pdf). Biogeosciences 5: 1295–1310. doi:10.5194/bg-5-1295-2008. .
[2] Orr, P. J.; Kearns, S. L. (2011). X-Ray Microanalysis of Burgess Shale and Similarly Preserved Fossils. 36. pp. 271–299.
doi:10.1007/978-94-007-0680-4_11.
[3] Goldstein, J. I. et al. (2003). Scanning Electron Microscopy and X-Ray Microanalysis (http:/ / books. google. com/ ?id=ruF9DQxCDLQC&
printsec=frontcover). Springer. ISBN 0306472929. .
[4] Study of EDS vs. WDS accuracy in common labs (http:/ / www. cameca. fr/ html/ epma_eds. html)
External links
• MICROANALYST.NET (http://www.microanalyst.net/index_e.phtml) - Information portal with X-ray
microanalysis and EDX contents
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EDX - Energy Dispersive X-ray Analysis or
EPMA - Electron Probe Micro Analysis
This technique is used in conjunction with SEM and is not a surface science technique. An electron beam strikes the
surface of a conducting sample. The energy of the beam is typically in the range 10-20keV. This causes X-rays to be
emitted from the point the material. The energy of the X-rays emitted depend on the material under examination. The Xrays are generated in a region about 2 microns in depth, and thus EDX is not a surface science technique. By moving the
electron beam across the material an image of each element in the sample can be acquired in a manner similar to SAM.
Due to the low X-ray intensity, images usually take a number of hours to acquire. Elements of low atomic number are
difficult to detect by EDX. The SiLi detector (see below) is often protected by a Beryllium window. The absorbtion of the
soft X-rays by the Be precludes the detection of elements below an atomic number of 11 (Na). In windowless systems,
elements with as low atomic number as 4 (Be) have been detected, but the problems involved get progressively worse as
the atomic number is reduced.
The Lithium drifted Silicon (SiLi) detector
The detector used in EDX is the Lithium drifted Silicon detector. This detector must be operated at liquid nitrogen
temperatures. When an X-ray strikes the detector, it will generate a photoelectron within the body of the Si. As this
photoelectron travels through the Si, it generates electron-hole pairs. The electrons and holes are attracted to opposite
ends of the detector with the aid of a strong electric field. The size of the current pulse thus generated depends on the
number of electron-hole pairs created, which in turn depends on the energy of the incoming X-ray. Thus, an X-ray
spectrum can be acquired giving information on the elemental composition of the material under examination.
The X-ray microcalorimeter detector
Recently, an exciting development in the field of EDX is the X-ray microcalorimeter. This device has a much higher energy
resolution (~3eV) than the traditional Si (Li) detector.