EDX module notes

Energy-dispersive X-ray microanalysis in the electron microscope

1. Introduction When a high-energy electron beam hits a specimen, X-rays characteristic of the atoms in the specimen are generated within the region illuminated. This allows the possibility of microanalysis, that is, the chemical analysis of a small amount of material, or a small part of a larger specimen. If we can measure the energy of the X-rays (or equivalently their wavelength, since they are related by Planck's constant, E = hc/ or specifically EkV = 12.4/Angstroms), then we can immediately tell qualitatively which elements are present in the part of the specimen under investigation. If we measure X-ray intensities, we also get an immediate rough idea of how much of each element is present. In certain cases, appropriate corrections allow us to determine the specimen composition quantitatively. The instrumental and specimen requirements for quantitative analysis are however much more stringent than for qualitative and semi-quantitative analysis, and so we shall concentrate here on the latter. Qualitative and semi-quantitative X-ray microanalysis is a common feature of SEMs and analytical TEMs, usually using energy-dispersive X-ray detectors. Quantitative microanalysis is most commonly performed in a microprobe, which is a purpose-built SEM-type instrument equipped with computer-controlled wavelength-dispersive (and sometimes also energy-dispersive) X-ray detectors. These instruments will also have features such as automatic stage drives and built-in software correction packages necessary for the routine, accurate analysis of large numbers of specimens. If you wish to carry out fully quantitative analyses, there are other courses that will cover this in more detail (Prof J M Titchmarsh's graduate lectures and the WDX and quantitative analysis module.)

2.

Generation of X-rays

A typical X-ray spectrum is shown in figure 2.1. It consists of a characteristic peaks superimposed on a background of "Bremsstrahlung".
spectrum 1

Counts

Fig 2.1 Typical EDX spectrum

0 1 2 3 4 5 6 7 Full Scale 3656 cts Cursor: -0.169 keV (0 cts)

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EDX module notes The Bremsstrahlung (braking radiation) is generated as the result of deceleration of high-energy electrons in the field surrounding the nucleus and inner-shell electrons. Since the incident electrons can lose any amount of their energy in this process, the energy distribution of the emitted X-rays is continuous (hence continuum). The closer the incident electron comes to hitting an atom, the stronger the interaction and the greater the energy likely to be lost. In the extreme case the electron may lose all of its energy in a single event: this gives an upper limit of the continuum equal to the incident beam energy (i.e. the microscope operating voltage). However a wide miss (giving a low energy loss) is more likely than a close miss (high energy loss), causing the background to rise steeply at lower energies until specimen absorption and detection inefficiencies cause a fall off below an energy of about 1kV. Bremstrahlung contains no useful information on the composition of the specimen, and a major step in quantification is to remove the background contribution from each characteristic peak. The characteristic peaks carry the compositional information. They arise when the energy of the incident electrons is high enough to eject inner-shell electrons from atoms in the specimen. For example, the ejection of a K-shell electron leaves the atom in an excited state. One of the ways it can lower its potential energy is by an electron from an outer shell falling to the vacant inner-shell position and at the same time emitting an X-ray of characteristic energy (figure 2.2).

Fig 2.2 Transitions leading to the generation of characteristic X-rays.

This characteristic energy is determined by the difference in the electron energy levels of the atom and therefore can provide direct information about the chemistry of the electron beam/specimen interaction volume. A variety of characteristic energy X-rays is generated as the various displaced inner-shell electrons are replaced by the various outer-shell electrons, If an electron is ejected from the K shell and this is filled by an electron from the L shell a K X-ray is emitted; if it is filled from the M shell a K X-ray is emitted. Similarly, if an electron is ejected from the L shell and an electron fills this from the M shell an L X-ray is emitted, if it is filled from the N shell an L X-ray is emitted. The energies of the strongest K and L lines for typical light, medium and heavy elements are shown below.

EDX module notes K

Be (Z = 4) Fe (Z = 26) Au (Z = 79) Fe Au

110 eV 6.4 keV 68.8 keV 0.70 keV 9.71 keV

The K lines are most commonly used for analysis of lighter elements. However, it is not always possible to excite the K-lines of heavier elements, since the threshold energy to eject a K-shell electron increases with atomic number. For example, elements heavier than tin (Z=50) require electrons of energy E >25keV to excite any K-lines at all, and the production is not efficient until E > 75keV. If we are using an SEM with a maximum electron energy of perhaps 30keV, we must use L-series X-rays in order to detect heavier elements, or even for very heavy elements M-series X-rays. The most efficient production of X-rays generally occurs when the bombarding electrons have about three times the X-ray energy. In fact, all elements have at least one strong X-ray line less than 10keV, and so analysis should be possible using an SEM operating at 30kV. Not every ionization event results in X-ray emission; the alternative process is the ejection of an Auger electron. This occurs when a characteristic X-ray is re-absorbed within the atom by an outer shell electron. The original characteristic X-ray will not be detected; instead a lower-energy characteristic energy X-ray will be created as the outer shell vacancy is filled. The ejected outer shell electron will have energy equal to the difference between the energy of the original characteristic X-ray and the binding energy of the ejected electron. These are Auger electrons. The probability of characteristic X-ray generation rather than Auger electron emission (the fluorescent yield) decreases rapidly with decreasing atomic number, see fig 2.3. The fluorescent yield is 0.764 for the Mo K shell, 0.381 for the Co K shell but only 0.047for the Si K shell.
1 0.1 0.01 0.001 0.0001 Yield 1E-05 1E-06 1E-07 1E-08 1E-09 1E-10 Atomic number (from Z = 1 to 40) K lines L lines M lines

Figure 2.3

X-ray fluorescent yield for elements from hydrogen to zirconium.

EDX module notes 3. Energy-dispersive X-ray spectrometry (EDX)

EDX usually employs solid-state detectors capable of measuring X-ray energies in a range 1-20kV. A typical EDX system is shown schematically in figure 3.1 It can be broken down into several components: a solid-state detector, X-ray processing circuits (preamplifier, pulse processor, energy to digital converter and multi channel analyser) and data management system (computer and software).

Fig 3.1 Schematic EDX system

The detector (shown schematically in greater detail in figures 3.2 and 3.3) sits as close to the specimen as is compatible with other requirements. Solid state detectors are usually made from single crystals of silicon, and are essentially p-i-n junctions operated in reverse bias. When an X-ray enters the active region of the detector crystal there is a high probability that it will be absorbed in an interaction with an electron of one of the silicon atoms producing a high-energy photoelectron. This photoelectron loses its energy in interactions that promote valence-band electrons to the conduction band leaving holes in the valence band. On average 3.8 to 3.9 eV are dissipated in the creation of each electronhole pair. The electron-hole pairs are swept in opposite directions by the electric field in the depletion region of the junction. Measuring the X-ray energy is just a matter of measuring the total charge created in the crystal during the absorption of the X-ray.

EDX module notes

X-rays pass through : collimator electron trap window gold layer dead layer into Li-drifted Si crystal

Fig 3.2 EDX detector actual layout

Fig 3.3 EDX detector The top diagram shows the detector schematically the shaded region is the lithiumdrifted Si.

The bottom diagram shows schematically the production of electron-hole pairs in the active region of the detector.

EDX module notes The crystal is operated as a reverse bias diode under an applied voltage of between 100 and 1000 volts. The free charge created within the diode leads to a temporary increase in the conductivity; this current is integrated with respect to time to give the total charge. This charge is extremely small; for example a CuK X-ray at 8.04kV will generate just over 2000 electron hole pairs giving a charge of just 3.3 x10-16 C. To reduce the residual conductivity of the crystal due to random thermal excitation of electrons across the band gap the crystal is operated at low temperature, as close to liquid nitrogen temperature as possible hence the liquid nitrogen dewar attached to the column, which is the most obvious outward sign that an EDX system is fitted to the microscope. The extremely small charge is initially amplified by a preamplifier positioned as close to the crystal as possible, also operating at low temperature, to minimise noise on the signal. As most crystal impurities contribute to the conductivity of silicon by creating a source of excess holes, lithium is drifted into the crystal to compensate for the native impurities present (and hence such detectors are called lithium-drifted silicon (SiLi) detectors). This produces the wide intrinsic depletion region in the p-i-n sandwich, forming the active region of the detector. The detector is usually carefully collimated to ensure that only X-rays generated at the specimen are detected. The nitrogen-cooled crystal is kept under vacuum with a thin window to separate the detector from the microscope vacuum system (which can be vented). A gold contact layer is used to make electrical contact to the crystal surface. There is a region of crystal, where the lithium has not drifted, which contains excess holes and hence will not collect charge properly: this is called the dead layer. There is often an electron trap to prevent back scattered or secondary electrons hitting the crystal (particularly on SEMs). The window, gold contact layer and Si dead layer all absorb X-rays before they can be detected, with the absorption being greater for lower energy X-rays. It is possible to get 'windowless' detectors that are kept in their own vacuum system and inserted into the microscope through a valve interlocked to the microscope vacuum system. It is now more usual to use an 'atmospheric thin window' detector where the window is very thin, low atomic weight, material (hydrocarbon) which is aluminised to avoid charging and mounted on a micro-machined silicon support. However, the efficiency of detection for X-rays with energies much below 800V is always poor. Standard Be window detectors will not detect X-rays with energies below about 1kV, ie. elements with atomic numbers below 11 (Na). If an X-ray has a high energy it is possible that all of its energy may not be dissipated in the active region of the crystal : this leads to incomplete charge collection. EDX spectrometers work best in the region 1 to 20keV for these reasons.

EDX module notes

4.

X-ray processing

Most EDX detectors use a pulsed optical feedback circuit. In this design the output of the preamplifier FET is allowed to range between pre-set limits at a rate controlled by the residual leakage current of the crystal. Upon reaching the upper limit, an LED shines on the FET to reset the circuit (using the photoelectric response of the FET). This produces a saw tooth ramp output of the preamplifier: the better the crystal, the longer the ramp time. When an X-ray is absorbed in the crystal there is a step increase in the ramp, the magnitude of which is proportional to the total charge produced. The next step in the processing is to condition the pulse for acceptance by an analogueto-digital converter, preserving the information contained in the pulse while filtering out noise. Filters can be characterised by their time constant, the longer the time constant the less sensitive the filter to high frequency noise and the more accurately the processor can determine the charge created by the X-ray. Naturally the longer the time constant, the longer it takes to process the charge. There is a trade off between the rate at which X-rays can be processed (throughput) and the accuracy (spectral resolution). Each signal pulse must be measured individually with reference to a zero level. A pulse cannot be measured if it is superimposed upon another, nearly coincident, pulse. Pulse pile up rejection circuits discriminate the signal to determine the beginning of each pulse and calculate when interfering overlaps have occurred. Both pulses are then rejected. They also determine if the pulse is higher than the maximum of the energy range: if so the pulse is rejected without measurement of its energy. The remaining pulses are considered valid and their energies are measured. They are passed to the energy to digital converter, their height is measured and assigned to an energy channel in the multi channel analyser (MCA). The number of counts in that channel is then increased by one. The spectrum assembled by the MCA is displayed on the screen of a computer, which also allows the analyst to manipulate the display or use various software packages to assist in the analysis of the data. Obviously there are times when the detector does not count X-ray pulses, particularly if more than one pulse is detected almost coincidentally. This is known as dead time, usually expressed as a percentage. The time for which the processor is actually counting is known as the livetime, usually expressed in seconds. The chronological time it takes for an acquisition is known as the realtime. For a given X-ray detection rate (input count rate) the dead time will increase with longer processing time giving a lower output count rate (figure 4.1), but the spectral resolution will improve. There is a trade off between the input count rate, the processing time, deadtime, spectral resolution and output count rate. The analyst has control of the input count rate, by adjusting the incident beam current or the specimen to detector distance, and of the processing time if spectral resolution can be sacrificed.

EDX module notes

Generally the processing time will be set to give the desired spectral resolution and the incident beam adjusted to give a reasonable count rate so that a statistically meaningful spectrum can be collected within a reasonable realtime. As a guide the maximum throughput occurs when the deadtime is about 60% of the realtime.

Figure 4.1. Effect of processing time and count rate on deadtime. Data management and display. The data in the MCA is displayed as a histogram, of the number of counts in each energy channel, on a computer display. The computer is also the user interface to control the detector, allowing the analyst to set acquisition parameters, stop and start acquisitions, store and print spectra, change the display or the range of the MCA. It also allows the analyst to carry out data analysis (e.g. peak recognition, corrections and quantitative analyses) by the use of proprietary software. 5. Spatial resolution in X-ray analysis

X-rays generated deep in a specimen can escape and be detected. The volume of the specimen from which the detected X-rays originate (sampling volume) is therefore almost as large as the interaction volume.

EDX module notes

Fig 5.1. The interaction volumes for thin foils and bulk specimens

For bulk specimens (see figure 5.1) the interaction volume is smallest for low energy electrons and heavy elements, but is difficult to make smaller than about 1m x 1m x 1m without reducing the energy of the beam to the point where no useful X-rays are generated. This then determines the spatial resolution in SEM or microprobe analysis. In thin-film analysis, however, the sampling volume is much smaller, and is essentially determined by the electron probe diameter if the foil is sufficiently thin that beamspreading is negligible (figure 5.1). It is therefore possible to obtain analyses from regions as small as 10nm or even less. Since the sampling volume is so small, the X-ray signal will also be small and noise will be a problem. Some specialised instruments such as our FEGSTEM use very bright field-emission electron sources in order to maximise the current in the fine probe. 6. Energy Resolution in EDX.

Characteristic X-ray peak broadening occurs for several reasons: the accuracy of determining the X-ray energy; noise in the external circuitry; and the statistical distribution of X-ray losses between ionisation and crystal losses. The first two factors are heavily influenced by the instrumentation. The equipment manufacturer aims to optimize energy resolution by design of the detector and the electronic circuitry. The analyst can choose an appropriate processing time, in order to optimise the energy resolution for the particular experiment being carried out. However, earthing and the positioning of equipment and cables can have a large effect on the external noise picked up by the system and great care must be taken on installation of this type of equipment. 9

EDX module notes

The width of a characteristic X-ray peak is given by the equation: FWHM = [N2 +5.5FE] 1/2 where: N = electronic noise in the system (90eV for older detectors, 40eV for newer detectors) F = Fano factor (0.11 for Si) = Energy to produce an electron hole pair (3.8eV) E = X-ray line energy Typical values for modern detectors are 133eV for Mn K and 60eV for O K. It must be noted that in general EDX peaks are much broader than in WDX. If there is a severe problem with peaks of different elements in the specimen overlapping WDX will have a far better chance of deconvoluting the peaks.

7.

Spectral artefacts in EDX

Spectral artefacts fall into two categories, those generated by the microscope, and those generated by the EDX system. Effects due to the microscope often pose the greatest problem to the analyst, because they are often difficult to recognise and eliminate. It is possible for X-rays to be generated from areas other than the area of interest, and by a source other than the primary beam. Such spurious X-rays are generally of greater concern in an analytical TEM than an SEM because of the higher operating voltage. The major areas from which spurious X-rays are generated include the illumination system, and the microscope stage and specimen. Stray electrons around the condenser apertures, as well as hard X-rays generated at the second condenser aperture, can interact with the specimen and generate X-rays at a point well away from the area of interest. Manufacturers generally supply special thick "top-hat" apertures which minimise this problem, but which may not eliminate it altogether. It is essential to carry out a "hole count", ie place the beam in a hole in the specimen, and observe if any specimen-characteristic spectrum is detectable. In a well set-up microscope, the hole count should be very small. Also it is generally assumed that the incident beam has a well-defined Gaussian intensity profile, whereas, particularly for the smallest probes, there are often large numbers of electrons outside the presumed beam area. It is important to align the instrument properly and set up small probes carefully to avoid this effect. Effects from the stage region are more insidious in that they are less easy to specifically define and remove. Spurious X-rays may be generated from the lower objective polepiece, the specimen holder or other adjacent microscope components, and by interaction of the specimen with its own Bremsstrahlung. Transmitted electrons may be scattered and strike the lower pole piece or objective apertures. Again these artefacts are

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EDX module notes worse in a TEM than in an SEM due to the restricted space available, the higher operating voltage, and the effects of transmitted electrons from the thin film specimen. They can be minimised by good design of microscope and special analytical specimen holders. Any of these extra X-ray signals could enter the EDX detector, although the manufacturers fit collimators to the front of the detectors to try to prevent collection of X-rays from anywhere except the beam/specimen interaction volume. These artefacts can be further reduced by use of low Z shields on the pole pieces and around the specimen. Manufactures often fit carbon-coated shields to the pole pieces and special EDX specimen holders made of carbon, beryllium and aluminium are available. TEM users should be aware of the detrimental effect of using a standard objective aperture mechanism. Low Z shielded or special EDX apertures, which are not directly below the specimen but positioned in a conjugate plane lower in the column are available for some instruments. Spectral artefacts produced by the EDX system include incomplete charge collection, escape peaks and sum peaks. Incomplete charge collection occurs when not all of the energy of an X-ray is lost in the active region of the crystal. The effect of incomplete charge collection on the spectrum is an increased background on the low energy side of a characteristic X-ray peak. The problem is worst for X-ray peaks of higher energy, close to 20keV. Escape peaks occur when a Si X-ray produced by fluorescence escapes the detector, leading to an artefact peak at an energy equal to the energy of the parent minus the energy of the Si X-ray that is generated (mainly Si-K at 1.74 keV). The escape peak will generally be a very small proportion of the main peak and will only be visible for very high-count peaks. Sum peaks occur when two X-rays arrive at the detector nearly simultaneously, so that they are not discriminated by the pulse pile-up rejection electronics, giving a false peak at the sum of the two X-ray energies. The most important factor in avoiding this artefact is the speed of the processor discrimination circuits. The analyst can reduce the effect by reducing the count rate (X-ray signal strength). The software of many modern systems is designed to recognise and flag escape and sum peaks. Large (or high) deadtime is caused by the processing circuitry not being available to process the X-ray. This partly depends on the quality and speed of the processing electronics from the manufacturer. The higher the throughput (number of X-rays processed per second) the lower the deadtime for a given X-ray count rate and processing time. Assuming that the only signal seen by the detector is characteristic X-rays from the specimen, the deadtime is related to the processing time or the X-ray signal. Reducing the processing time or the incident beam current will reduce the deadtime. If high energy Xrays are generated in the illumination system these can add to the deadtime without registering on the spectrum, as they are above the energy range.

8.

Problems in the use of EDX systems

The more important include:

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EDX module notes

Peak broadening - the peak width in EDX is typically 150eV (FWHM), compared with the "natural" X-ray peak width of about 2eV. This may make resolving between two peaks separated by less than about 100eV difficult. Wavelengthdispersive systems offer significant advantages. It is difficult or impossible to analyse for light elements. Elements with Z 11 (Na) present few problems. However, problems arise with lighter elements for two reasons. First, the fluorescent yield (ie the proportion of ionization events which result in the emission of an X-ray rather than Auger electron) decreases with decreasing Z. Second, the low energy X-rays characteristic of light elements are absorbed in the Be window, in the Au contact layer, and in the Si "dead" layer. There are several approaches to try to circumvent the problem: (i) Use a windowless or ultra-thin window detector. These are said to be good for Z 6. They require a very good microscope vacuum or they quickly become contaminated. Remember also that soft X-rays may well be absorbed before they even leave the specimen, so that detection of say C in a buried carbide particle in a thin-foil specimen is unrealistic. C may well be detected, but it will almost certainly come from a surface contamination layer! (ii) Wavelength-dispersive spectrometers can detect and quantify elements with Z 4 , but only in bulk specimens. (iii) Use Electron Energy Loss Spectroscopy (EELS). The primary ionization event, when an incident electron ejects an orbital electron from an atom by an inelastic scattering process, requires a finite and characteristic minimum amount of energy termed the critical excitation energy of the shell (Ec). Conservation of energy requires that the incident electron lose a corresponding amount of energy. In EELS we measure these energy losses using a magnetic spectrometer. Details are beyond the scope of this course (but there are EELS modules). We note however two advantages of EELS over EDX for light-element analysis. First, the primary energy loss process is independent of whether the excited atom subsequently emits an X-ray or an Auger electron, so the very small fluorescent yields for light elements are of no consequence. Second, the geometric collection efficiency in EELS can be as high as 80%, compared with typically 2% for an EDX detector. 9. New detectors A new generation of silicon drift detectors is now reaching the market, capable of much higher count rates than SiLi detectors. A schematic of such a detector is shown below in figure 9.1

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EDX module notes

Fig 9.1: silicon drift detector

The X-rays enter the detector from below in this figure. .An electric field with a strong component parallel to the surface drives electrons generated by the absorption of X-rays towards a small collecting anode. The electric field is generated by a number of increasingly reverse biased field strips covering the top surface of the device. The unique property of this detector is the extremely small anode capacitance, which allows count rates up to 30k counts per second. They also work with moderate cooling Peltier cooling can be used, so there is no need for liquid nitrogen. 10. Practical considerations

The following is a brief summary of points made previously as a checklist for the analyst. a) Can the detector see the specimen? Think about the geometry, tilt the specimen towards the detector, check for obstructions. b) Is the count rate appropriate (20% to 40% is good, never above 60%)? Adjust the processing time for a suitable energy resolution, adjust incident beam current or detector position to change the input count rate. c) Are you analysing just the feature of interest? Is there a problem with high energy Xrays or electrons from the illumination system (hole count)? Is the incident beam well defined? Consider beam spreading and the excitation volume. Adjust the HT if appropriate. Are you analysing X-rays from the matrix around or below the object of interest? d) Is the incident beam hitting the objective apertures in TEM? e) Does the spectrum give results that you can accept? Are the peaks you expect present, does the spectrum tail off at the low energy end (absorption)? f) Can you explain all the peaks in the spectrum? Are there escape or sum peaks? Are other peaks from the specimen or from elsewhere in the instrument?

S Lozano-Perez (After M L Jenkins)

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