Particles depth profiling

Because a FIXE spectrum represents the int al of all the X rays created along the particle s path, a single FIXE measurement does not provide any depth profile information. All attempts to obtain general depth profiles using FIXE have involved multiple measurements that varied either the beam energy or the angle between the beam and the target, and have compared the results to those calculated for assumed elemental distributions. Frofiles measured in a few special cases surest that the depth resolution by nondestructive FIXE is only about 100 nm and that the absolute concentration values can have errors of 10-50%. 

Three common uses of RBS analysis exist quantitative depth profiling, areal concentration measurements (atoms/cm ), and crystal quality and impurity lattice site analysis. Its primary application is quantitative depth profiling of semiconductor thin films and multilayered structures. It is also used to measure contaminants and to study crystal structures, also primarily in semiconductor materials. Other applications include depth profilii of polymers, high-T superconductors, optical coatings, and catalyst particles. ... 

Like XPS, the application of AES has been very widespread, particularly in the earlier years of its existence more recently, the technique has been applied increasingly to those problem areas that need the high spatial resolution that AES can provide and XPS, currently, cannot. Because data acquisition in AES is faster than in XPS, it is also employed widely in routine quality control by surface analysis of random samples from production lines of for example, integrated circuits. In the semiconductor industry, in particular, SIMS is a competing method. Note that AES and XPS on the one hand and SIMS/SNMS on the other, both in depth-profiling mode, are complementary, the former gaining signal from the sputter-modified surface and the latter from the flux of sputtered particles. 

Eor analysis of emitted particles, solid state surface barrier detectors (SBD) are used inside the scattering chamber to measure the number and energy of the reaction products. Stopper foils are used to prevent scattered projectiles from reaching the detector. Depth profiles can be obtained from the energy spectra, because reaction products emitted in deeper layers have less energy than reaction products emitted from the surface. The concentration in the corresponding layer can be determined from the intensity of reaction products with a certain energy. 

The cross-section curve a(E) gives the dependence of the nuclear cross-section on the projectile energy, E. The measured energy spectra of emitted particles or the excitation curve N(Eq) wiU depend on the depth profile N(x) of the analyzed isotope and on the cross-section curve (t(E(x)), where E(x) gives the energy of the projectiles at a depth x. Evaluation of the depth profile N (x) from measured energy spectra or excitation curves often requires a tedious evaluation procedure if the cross-section curve has a complex structure. It is simplified for two special types of behavior of the cross-section curve ... 

Figure 1. Three levels of analysis for catalyst materials, a) bulk analysis of an entire catalyst pellet, b) surface analysis and depth profiling from the surface inward, c) analytical electron microscopy of individual catalyst particles too small for analysis by other techniques.

The electron interaction between nanosized gold particles and iron oxide support is only one factor which determines the properties of the gold/oxide system. For instance, in the Au/FeO,c/Si02/Si(l 0 0) model sample the depth profile (after successive Ar ion bombardment at a... 

The use of nuclear techniques allows the determination of C, N, H, O, and heavier contaminants relative fractions with great accuracy, and of the elements depth profile with moderate resolution (typically 10 nm). Rutherford backscattering spectroscopy (RBS) of light ions (like alpha particles) is used for the determination of carbon and heavier elements. Hydrogen contents are measured by forward scattering of protons by incident alpha particles (ERDA) elastic recoil detection analysis [44,47]. 

Since the nuclear and electronic scattering cross sections for alpha particles are well known, the relative concentrations of the elements and their depth profiles can be easily obtained. The relative element concentrations are determined by the relative scattering intensities. The depth profile is obtained from the energy spread of the scattered particles, which lose energy before and after the nuclear collision, by inelastic scattering with electrons. The knowledge of the elements areal density and of the film thickness allows the determination of film density. 

The data chain of the collected atoms can be converted to a one-dimensional composition-depth profile. The depth profile shows an average concentration of solute within the aperture, and there is always a possibility that the chemical information from the selected area is a convolution of more than one phase, as indicated diagrammatically in Figure 1.5, which represents the analysis of a FIM specimen containing second phase particles and also an interface across which there is a change of composition. 

RBS is a quantitative analytical tool which provides simultaneously the depth profile and the composition by mass number of the sample. The disadvantage is that a large and expensive particle accelerator is required to produce the incident beam. The probe depth of RBS is typically 1-2 pm with a depth resolution of 20-30 nm. 

Depth profiling of a solid sample may be performed by varying the interferometer moving-mirror velocity (modulated IR radiation). By increasing the mirror velocity, the sampling depth varies, and surface studies may be performed. Limitations do exist, but the technique has proven to be quite effective for solid samples [21]. In addition, unlike diffuse reflectance sampling techniques, particle size has a minimal effect upon the photoacoustic measurement. 

Solution of equation (10) which involves sedimentation in the presence of mixing and that of equation (11) which contains the sedimentation term only, are exponential in nature. The major conclusion which arises from this is that the logarithmic nature of the activity-depth profiles by itself is not a guarantee for undisturbed particle by particle sediment accumulation, as has often been assumed. The effects of mixing and sedimentation on the radionuclide distribution in the sediment column have to be resolved to obtain pertinent information on the sediment accumulation rates. (It is pertinent to mention here that recently Guinasso and Schink [65] have developed a detailed mathematical model to calculate the depth profiles of a non-radioactive transient tracer pulse deposited on the sediment surface. Their model is yet to be applied in detail for radionuclides. )... 

A quantitative and fairly easy method to obtain particle reworking rates in deep sea sediments became possible after the elegant work of Nozaki et al., [68] based on 210Pb distribution in them. The radioactive half-life of 210Pb is too short (22.6 yrs) to produce measurable depth profiles in deep sea sediments based on sedimentation alone since its activity would be limited to the top 1 mm layer. In such a case its depth profile predominantly records the effects of particle reworking and its distribution can be approximated as ... 

UPS studies of supported catalysts are rare. Griinert and coworkers [45] recently explored the feasibility of characterizing polycrystalline oxides by He-II UPS. A nice touch of their work is that they employed the difference in mean free path of photoelectrons in UPS, V 2p XPS and valence band XPS (below 1 nm, around 1.5 nm, and above 2 nm, respectively) to obtain depth profiles of the different states of vanadium ions in reduced V205 particles [45]. However, the vast majority of UPS studies concern single crystals, for probing the band structure and investigating the molecular orbitals of chemisorbed gases. We discuss examples of each of these applications. 

Dynamic SIMS is used for depth profile analysis of mainly inorganic samples. The objective is to measure the distribution of a certain compound as a function of depth. At best the resolution in this direction is < 1 nm, that is, considerably better than the lateral resolution. Depth profiling of semiconductors is used, for example, to monitor trace level elements or to measure the sharpness of the interface between two layers of different composition. For glass it is of interest to investigate slow processes such as corrosion, and small particle analyses include environmental samples contaminated by radioisotopes and isotope characterization in extraterrestrial dust. 

As mentioned, the type of concentration-depth profiles observed in oceans should also be observed in lakes. However, the vertical concentration differences in lakes are often not as pronounced as in the ocean. The reason for this is, that the water column in lakes is much shorter mixing and stagnation in lakes is much more dynamic than in the oceans. Due to the presence of high concentrations of different particles in lakes, the release of trace elements from biogenic particles may not be clearly observed, due to readsorption to other particles. This would mean that low concentrations are observed throughout the water column, but that concentration differences are small. Atmospheric inputs to the upper water layers may also make it more difficult to observe a depletion of certain elements in the epilimnion. 

The results of concentration measurements are presented as vertical profiles similar to those for the water column, with the vertical axis representing increasing depth below the sediment-water interfece. Depth profiles of concentrations can be used to illustrate downcore variations in the chemical composition of pore waters or in the solid particles. Dissolved concentrations are typically reported in units of moles of solute per liter of pore water. Solid concentrations are reported in mass/mass units, such as grams of carbon per 100 grams of dry sediment (%C) or mg of manganese per kg of dry sediment (ppm Mn). 

Neutron depth profiling technique (NDP) [13]. NDP is a speeial method for depth profiling of few light elements, namely He, Li, B and N in any solid material. The method makes use of speeifie nuelear reaetions of these elements with thermal neutrons. The samples are plaeed in the neutron beam from nuclear reactor and the charged products of the neutron indueed reactions (protons or alpha particles) are registered using a standard multiehannel spectrometer. From the measured energy spectra the depth profiles of above mentioned elements can be deduced by a simple computational procedure. 

Figure 18. Depth profiles of hydrogen from polyimide (PI) implanted with 100 keV Kr ions to the fluences indicated. The horizontal line shows the hydrogen concentration in pristine PI. The profiles were determined from ERDA measurement performed with 2 MeV alpha particles [122]. The depth resolution was about 50 nm. It is seen that significant H depletion starts at the fluence of about IxlO " cm. ...

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