Energy Dispersive X-Ray (EDX) Analysis

Generation of X-Rays The displacement of target material electrons by primary electrons triggers the release of an x-ray photon, which is characteristic of the atom (element) from which it was released. Atoms hold electrons in orbit around their nuclei as a result of electrical charge differences between them, the nucleus carrying a positive charge and the electrons carrying a negative charge. These charges exactly balance each other. The arrangement of electrons around the nucleus of an atom is conventionally considered as a sequence of 'electron shells', with the innermost shell electrons possessing the lowest energy but with higher bonding energies, and the outermost electrons possessing the highest energies with lower binding energies. The shells are, also conventionally, labeled K, L, M, N, O, P, and Q from innermost to outermost. Because of the differing binding energy levels of the electrons around the nucleus, primary electrons of a higher potential energy (electron volts - eV) are required to displace Kshell electrons than are required to displace L-shell electrons, which is higher than that required for M-shell electrons etc. A simple diagram of the first three shells is illustrated below-

Primary electrons bombarding the atom are able to 'knock' shell electrons out of their orbits, which can be replaced by electrons from shells further out, that are able to 'jump' into the inner shell vacancies. There are a number of reactions that occur as a result of this, but for the purposes of explaining the generation of x-rays, only the following points are considered. The knocking out of an inner shell electron causes the atom to take on an excited, high energy state until the missing electron is replaced and the atom relaxes. There is therefore a difference in energy states. This difference can be large, and if it is, the excess energy can be released in the form of an x-ray (it can also be released in the form of an Auger electron, but is not considered here), which carries this energy difference, and has a wavelength that is characteristic of the atomic species from which it came. The following diagram is an illustration of this-

It should be noted that replacement of L and M shell (etc.) electrons can also be achieved by electrons jumping in from shells that are further out again, and can lead to a large number of generated x-rays of differing wavelengths. There are therefore a number of possible lines of x-rays available for analysis, but again this is not considered here, and references should be made to a relevant textbook for further details.
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Analysis of X-Rays The most significant issue to note from this is that the x-rays generated from any particular element are characteristic of that element, and as such, can be used to identify which elements are actually present under the electron probe. This is achieved by constructing an index of x-rays collected from a particular spot on the specimen surface, which is known as a spectrum. An example spectrum for phosphorous with fluorine. The element peaks for analysis have been marked in red. Where two peaks are shown for the same element, the smaller peak corresponds to one of the other lines of

electron replacement, such as an 'M' shell electron jumping into the 'K' shell. The y-axis is an arbitrary pixel count.

(example spectrum taken from the Oxford Instruments INCA software.)

The x-axis of the spectrum is the x-ray energy scale, along which x-rays collected from various elements are registered, and which in turn form a series of peaks along the xaxis where each peak corresponds to a particular element. With modern software, it is possible to collect a series of spectrums for each point (pixel) analysed by the electron beam probe, as it is scanned across the surface of the specimen. If one spot only is analysed, quantification of the relative proportions of elements under that spot is possible, which is known as point analysis. If however a line of pixels is analysed, a line-traverse analysis can be performed which can highlight changing proportions of elements with distance along the line. This is known as line scanning. Finally, each pixel in an image can also be analysed, which illustrates the distribution of a chosen element across the image. This is known as dot-mapping of the elements, and can take up some considerable time as the electron probe is required to dwell on each separate point for a pre-determined period of time in order to collect enough data for analysis. In many applications of the technique to concrete petrography this is normally done in conjunction with a backscattered electron image, where each pixel of the image has an exact and corresponding pixel on each of the element maps, which are collected at the same time and at the same resolution. Another reason for choosing this image type is that efficient x-ray analysis requires a flat polished surface where there are few obstructions to x-rays leaving the surface of the specimen that may cause contamination of the signal. The software requires calibration to known standards before normal use.

X-ray detector The group's Apollo 300LV FEGSEM is equipped with an Oxford Instruments INCA Energy X-ray detector and micro-analysis system, which is able to perform each of the above forms of analysis.

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Point Analysis In this technique, an image of the area for investigation is first captured, and the exact point for analysis is determined by the operator. The software is used to identify this point, and data capture can begin. With modern software, it is possible to identify multiple points on the specimen surface for analysis, either randomly selected or according to a pre-determined pattern (i.e. at intersections of a grid overlay or along a line). The software can then be set and left running to capture data automatically leaving the operator free to perform other functions. This is a standard feature and can be used in each of the three analytical variations. Example image showing points selected for microanalysis.
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To follow

Line Scanning Line scanning is useful for investigating the change in elements along a line of traverse on the specimen surface. Each pixel along the line is analysed and contains its own

spectrum of data for selected elements. It is therefore possible to plot a series of individual line plots, showing the intensity of elements along the length of the line. The lines themselves can be placed at any position on the image, between any two points, and for any length up to the total available image dimension. Line point analysis data collection is very quick and large amounts of data can be collected over a relatively short period of time. Example image showing line traverse Line plot for elements analysed in above image along length of traverse
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To follow To follow

Dot-Mapping As mentioned above this technique is used to analyse the distribution of elements in an image. Having selected the elements for analysis, an image resolution setting is selected, and then the data collection begins. Selection of image resolution is important as the time required to collect data in this technique is significantly longer than for point or line analysis. Higher resolution images will require more time than lower resolution images. For example, an image whose dimensions are double those of another will capture four times as much data and consequently take four times as long to capture the same amount of data. Large amounts of data are captured anyway, and stored as separate element intensity images, which are not greyscale images. However, a standard greyscale image of the analysis area is normally captured in tandem with the element intensity images, or 'dot-maps' (see below). This has many advantages in later image analysis operations, as each of the images can be used in any arithmetic combination, with any of the other images during analytical image algorithms. It is therefore possible to 'reconstruct' many of the phases and features present in the greyscale image based on compositional element data. A backscattered electron image of a concrete surface with a selection of elemental dot maps covering the same area. The concrete was manufactured using basalt coarse aggregate, with silica sand (quartz) for fine aggregate and is 3 days old. See the BEI pages for details on image formation. Different minerals (phases) within the coarse aggregate particle (upper left portion of image) are represented by areas of varying shades of grey. The quartz sand particles, of which there are three in the lower right area of the image, are of an even grey shade indicating homogeneity of composition (in this case Si). The smaller brighter particles in the interstitial region are un-hydrated particles of cement which are rich in Ca, with BEI

a poorly developed matrix of calcium silicate hydrate (C-SH) hardened cement paste. The black regions are resin filled voids. Field of view is approx. 0.7mm and the image size (resolution) is 256 pixels x 192 pixels. Al Ca

Fe

Mg

Si

Na

Ti

Energy-dispersive X-ray spectroscopy

Energy dispersive X-ray spectroscopy (EDS, EDX or EDXRF) is an analytical technique used for the elemental analysis or chemical characterization of a sample. As a type of spectroscopy, it relies on the

investigation of a sample through interactions between electromagnetic radiation and matter, analyzing xrays emitted by the matter in response to being hit with the electromagnetic radiation. Its characterization capabilities are due in 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 each other. To stimulate the emission of characteristic X-rays from a specimen, a high energy beam of charged particles such as electrons or protons, 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 form which they were emitted, this allows the elemental composition of the specimen to be measured.

Contents
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1 Equipment: the connection with SEM 2 Technological Variants 3 Accuracy of EDS 4 Emerging Technology 5 See also 6 External links
[edit]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-EDX) andelectron 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 intovoltage signals; this information is sent to a pulse processor, which measures the signals and passes them onto an analyzer for data display and analysis. [edit]Technological

Variants

Principle of EDX

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. 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 is much finer spectral resolution than EDS. WDS also largely 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. [edit]Accuracy

of EDS

Accuracy of EDS spectrum can be affected by many variants. Windows in front of the SiLi detector can absorb lowenergy X-rays(a.k.a. EDS detectors cannot detect presence of oxygen, carbon, boron, etc.). Differing the overvoltage of the EDS will result in different peak sizes - Raising over-voltage on the SEM will shift the spectrum to the larger energies making higher-energy peaks larger while making lower energy peaks smaller. Also many elements will have overlapping peaks (ex. Ti K and V K, Mn K and Fe K). Study of EDS vs. WDS accuracy in common labs 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 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 inhomogenous and rough samples. [edit]Emerging

Technology

There is a trend towards a newer EDS detector, called the Silicon Drift Detector (SDD). The SDD consists of a highresistivity 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) High count rates and processing 2) Better resolution than traditional SiLi detectors at high count rates 3) Lower dead time (time spent on processing x-ray event) 4) Faster analytical capabilities and more precise X-ray maps or particle data collected in seconds and 5) Ability to be stored and operate 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 (40mm sq. 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 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 calorimeters 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.