Electron-beam analysis

Loretto, M.H. 1984 Electron Beam Analysis of Materials. (Chapman and Hall, London). 

Bradley J. P. and Brownlee D. E. (1986) Cometary particles thin sectioning and electron beam analysis. Science 231, 1542-1544. 

Electron microscopy is one example of electron beam analysis of polsrmers and PMC. Beam charging effects occur in most polymers and PMC (99), imless when coated with a thin conductive layer (carbon, gold, or platinum). Environmental scanning electron microscopes (ESEM) do not require such coatings (100). Size and shape of the test object and possible electron beam heating effects then decide whether the method is NDT... 

The wavelength dispersive X-ray analyzer is more difficult to operate and requires a higher energy electron beam. Analysis time canbe lengthy (minutes rather than seconds for EDS) and multiple detectors must be used if more than a few elements are to be analyzed. The positive aspects... 

Edx is based on the emission of x-rays with energies characteristic of the atom from which they originate in Heu of secondary electron emission. Thus, this technique can be used to provide elemental information about the sample. In the sem, this process is stimulated by the incident primary beam of electrons. As will be discussed below, this process is also the basis of essentially the same technique but performed in an electron spectrometer. When carried out this way, the technique is known as electron microprobe analysis (ema). 

Instmmentation for tern is somewhat similar to that for sem however, because of the need to keep the sample surface as clean as possible throughout the analysis to avoid imaging surface contamination as opposed to the sample surface itself, ultrahigh vacuum conditions (ca 10 -10 Pa) are needed in the sample area of the microscope. Electron sources in tern are similar to those used in sem, although primary electron beam energies needed for effective tern are higher, typically on the order of ca 100 keV. 

Electron Microprobe A.na.Iysis, Electron microprobe analysis (ema) is a technique based on x-ray fluorescence from atoms in the near-surface region of a material stimulated by a focused beam of high energy electrons (7—9,30). Essentially, this method is based on electron-induced x-ray emission as opposed to x-ray-induced x-ray emission, which forms the basis of conventional x-ray fluorescence (xrf) spectroscopy (31). The microprobe form of this x-ray fluorescence spectroscopy was first developed by Castaing in 1951 (32), and today is a mature technique. Primary beam electrons with energies of 10—30 keV are used and sample the material to a depth on the order of 1 pm. X-rays from all elements with the exception of H, He, and Li can be detected. 

Elemental chemical analysis provides information regarding the formulation and coloring oxides of glazes and glasses. Energy-dispersive x-ray fluorescence spectrometry is very convenient. However, using this technique the analysis for elements of low atomic numbers is quite difficult, even when vacuum or helium paths are used. The electron-beam microprobe has proven to be an extremely useful tool for this purpose (106). Emission spectroscopy and activation analysis have also been appHed successfully in these studies (101). 

Electron Beam Techniques. One of the most powerful tools in VLSI technology is the scanning electron microscope (sem) (see Microscopy). A sem is typically used in three modes secondary electron detection, back-scattered electron detection, and x-ray fluorescence (xrf). AH three techniques can be used for nondestmctive analysis of a VLSI wafer, where the sample does not have to be destroyed for sample preparation or by analysis, if the sem is equipped to accept large wafer-sized samples and the electron beam is used at low (ca 1 keV) energy to preserve the functional integrity of the circuitry. Samples that do not diffuse the charge produced by the electron beam, such as insulators, require special sample preparation. 

X-Ray Emission and Fluorescence. X-ray analysis by direct emission foUowing electron excitation is of Hmited usefulness because of inconveniences in making the sample the anode of an x-ray tube. An important exception is the x-ray microphobe (275), in which an electron beam focused to - 1 fim diameter excites characteristic x-rays from a small sample area. Surface corrosion, grain boundaries, and inclusions in alloys can be studied with detectabiHty Hmits of -- 10 g (see Surface and interface analysis). 

In Surface Analysis by Laser Ionization (SALI), a probe beam such as an ion beam, electron beam, or laser is directed onto a surfiice to remove a sample of material. An untuned, high-intensity laser beam passes parallel and close to but above the sur-fiice. The laser has sufficient intensity to induce a high degree of nonresonant, and hence nonselective, photoionization of the vaporized sample of material within the laser beam. The nonselectively ionized sample is then subjected to mass spectral analysis to determine the nature of the unknown species. SALI spectra accurately reflect the surface composition, and the use of time-of-flight mass spectrometers provides fast, efficient and extremely sensitive analysis. 

The incoming electron beam interacts with the sample to produce a number of signals that are subsequently detectable and useful for analysis. They are X-ray emission, which can be detected either by Energy Dispersive Spectroscopy, EDS, or by Wavelength Dispersive Spectroscopy, WDS visible or UV emission, which is known as Cathodoluminescence, CL and Auger Electron Emission, which is the basis of Auger Electron Spectroscopy discussed in Chapter 5. Finally, the incoming... 

Overall a customer needs to know under what circumstances it is best to use either the electron-beam techniques of EDS and WDS or the X-ray technique of XRF for an analysis problem. If both are equally available, the choice usually resides in whether high spatial resolution is needed, as would be obtained only with electron-beam techniques. If liquids are to be analyzed, the only viable choice is XRF. If one s choice is to use electron-beam methods, the further decision between EDS and WDS is usually one of operator preference. That is, to commence study on a totally new sample most electron-beam operators will run an EDS spectrum first. If there are no serious peak overlap problems, then EDS may be sufficient. If there is peak overlap or if maximum sensitivity is desired, then WDS is usually preferred. Factored into all of this must be the beam sensitivity of the sample, since for WDS analysis the beam current required is lO-lOOx greater than for EDS. This is of special concern in the analysis of polymer materials. 

Cathodoluminescence (CL), i.e., the emission of light as the result of electron-beam bombardment, was first reported in the middle of the nineteenth century in experiments in evacuated glass tubes. The tubes were found to emit light when an electron beam (cathode ray) struck the glass, and subsequendy this phenomenon led to the discovery of the electron. Currendy, cathodoluminescence is widely used in cathode-ray tube-based (CRT) instruments (e.g., oscilloscopes, television and computer terminals) and in electron microscope fluorescent screens. With the developments of electron microscopy techniques (see the articles on SEM, STEM and TEM) in the last several decades, CL microscopy and spectroscopy have emerged as powerfirl tools for the microcharacterization of the electronic propenies of luminescent materials, attaining spatial resolutions on the order of 1 pm and less. Major applications of CL analysis techniques include ... 

Another basic approach of CL analysis methods is that of the CL spectroscopy system (having no electron-beam scanning capability), which essentially consists of a high-vacuum chamber with optical ports and a port for an electron gun. Such a system is a relatively simple but powerful tool for the analysis of ion implantation-induced damage, depth distribution of defects, and interfaces in semiconductors. ... 

As mentioned earlier, CL is a powerful tool for the characterization of optical properties of wide band-gap materials, such as diamond, for which optical excitation sources are not readily available. In addition, electron-beam excitation of solids may produce much greater carrier generation rates than typical optical excitation. In such cases, CL microscopy and spectroscopy are valuable methods in identifying various impurities, defects, and their complexes, and in providing a powerful means for the analysis of their distribution, with spatial resolution on the order of 1 pm and less. ... 

In summary, CL can provide contactless and nondestructive analysis of a wide range of electronic properties of a variety of luminescent materials. Spatial resolution of less than 1 pm in the CL-SEM mode and detection limits of impurity concentrations down to 10 at/cm can be attained. CL depth profiling can be performed by varying the range of electron penetration that depends on the electron-beam energy the excitation depth can be varied from about 10 nm to several pm for electron-beam energies ranging between about 1 keV and 40 keV. 

Applications of CL to the analysis of electron beam-sensitive materials and to depth-resolved analysis of metal-semiconductor interfaces by using low electron-beam energies (on the order of 1 keV) will be extended to other materials and structures. 

The classical approach for determining the structures of crystalline materials is through diflfiaction methods, i.e.. X-ray, neutron-beam, and electron-beam techniques. Difiiaction data can be analyzed to yield the spatial arrangement of all the atoms in the crystal lattice. EXAFS provides a different approach to the analysis of atomic structure, based not on the diffraction of X rays by an array of atoms but rather upon the absorption of X rays by individual atoms in such an array. Herein lie the capabilities and limitations of EXAFS. 

The simplest diffraction measurement is the determination of the surface or overlayer unit mesh size and shape. This can be performed by inspection of the diffraction pattern at any energy of the incident beam (see Figure 4). The determination is simplest if the electron beam is incident normal to the surface, because the symmetry of the pattern is then preserved. The diffraction pattern determines only the size and shape of the unit mesh. The positions of atoms in the surface cannot be determined from visual inspection of the diffraction pattern, but must be obtained from an analysis of the intensities of the diffracted beams. Generally, the intensity in a diffracted beam is measured as a fimction of the incident-beam energy at several diffraction geometries. These intensity-versus-energy curves are then compared to model calculations. ... 

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