Depth profiling, analytical

For solids unique capability of differentiating surface from sub-surface and bulk phenomena. Analytical depth profiling possible. 

In studying solids the short mean free paths of electrons and their strong dependence on kinetic energy provides a means of differentiating surface from subsurface and bulk phenomena and hence analytical depth profiling by studying core levels... 

Application Depth profiling, imaging, trace and isotope analysis, micro-and nano-analytics Depth profiling, imaging... 

The analytical depth profiling for these systems (e.g. the polystyrene data is shown in Figure 5) revealed that the reaction is essentially confined to the topmost monolayer of material ( ). This is entirely reasonable in terms of the plasma chemistry since the most prominent reactive species is atomic oxygen f ich is expected to have an extremely short mean free path in hydrocarbon polymers. This serves as a very good example of the powerful nature of XPS when applied to the study of the surface modification of polymers. 

The most common application of dynamic SIMS is depth profiling elemental dopants and contaminants in materials at trace levels in areas as small as 10 pm in diameter. SIMS provides little or no chemical or molecular information because of the violent sputtering process. SIMS provides a measurement of the elemental impurity as a function of depth with detection limits in the ppm—ppt range. Quantification requires the use of standards and is complicated by changes in the chemistry of the sample in surface and interface regions (matrix efiects). Therefore, SIMS is almost never used to quantitadvely analyze materials for which standards have not been carefiilly prepared. The depth resoludon of SIMS is typically between 20 A and 300 A, and depends upon the analytical conditions and the sample type. SIMS is also used to measure bulk impurities (no depth resoludon) in a variety of materials with detection limits in the ppb-ppt range. 

Static SIMS is labeled a trace analytical technique because of the very small volume of material (top monolayer) on which the analysis is performed. Static SIMS can also be used to perform chemical mapping by measuring characteristic molecules and fiagment ions in imaging mode. Unlike dynamic SIMS, static SIMS is not used to depth profile or to measure elemental impurities at trace levels. 

Figure 3 Depth profiles of F implanted into 2000 A Si on Si02 la) SALI profile with Ar sputtering and 248-nm photoionization and (b) positive SIMS profile with O2 sputtering. Analytical conditions SALI, SiF profile) 7-keV Ar, 248 nm SIMS, F profile) 7-keV02 ...

An especially significant application of NRA is the measurement of quantified hydrogen depth profiles, which is difficult using all but a few other analytical techniques. Hydrogen concentrations can be measured to a few tens or hundreds of parts per million (ppm) and with depth resolutions on the order of 10 nm. 

NRA is an effective technique for measuring depth profiles of light elements in solids. Its sensitivity and isotope-selective character make it ideal for isotopic tracer experiments. NRA is also capable of profiling hydrogen, which can be characterized by only a few other analytical techniques. Future prospects include further application of the technique in a wider range of fields, three-dimensional mapping with microbeams, and development of an easily accessible and comprehensive compilation of reaction cross sections. 

Besides the conventional Grimm-type dc source, which has dominated the GD-OES scene for approximately 30 years, other discharge sources are well known. Among those are various boosted sources which use either an additional electrode to achieve a secondary discharge, or a magnetic field or microwave power to enhance the efficiency of excitation, and thus analytical capability none of these sources has, however, yet been applied to surface or depth-profile analysis. 

Because of the complex nature of the discharge conditions, GD-OES is a comparative analytical method and standard reference materials must be used to establish a unique relationship between the measured line intensities and the elemental concentration. In quantitative bulk analysis, which has been developed to very high standards, calibration is performed with a set of calibration samples of composition similar to the unknown samples. Normally, a major element is used as reference and the internal standard method is applied. This approach is not generally applicable in depth-profile analysis, because the different layers encountered in a depth profile of ten comprise widely different types of material which means that a common reference element is not available. 

In contrast with the dc source, more variables are needed to describe the rf source, and most of these cannot be measured as accurately as necessary for analytical application. It has, however, been demonstrated that the concept of matrix-independent emission yields can continue to be used for quantitative depth-profile analysis with rf GD-OES, if the measurements are performed at constant discharge current and voltage and proper correction for variation of these two conditions are included in the quantification algorithm [4.186]. 

The potential of LA-based techniques for depth profiling of coated and multilayer samples have been exemplified in recent publications. The depth profiling of the zinc-coated steels by LIBS has been demonstrated [4.242]. An XeCl excimer laser with 28 ns pulse duration and variable pulse energy was used for ablation. The emission of the laser plume was monitored by use of a Czerny-Turner grating spectrometer with a CCD two-dimensional detector. The dependence of the intensities of the Zn and Fe lines on the number of laser shots applied to the same spot was measured and the depth profile of Zn coating was constructed by using the estimated ablation rate per laser shot. To obtain the true Zn-Fe profile the measured intensities of both analytes were normalized to the sum of the line intensities. The LIBS profile thus obtained correlated very well with the GD-OES profile of the same sample. Both profiles are shown in Fig. 4.40. The ablation rate of approximately 8 nm shot ... 

This area of research is still at its beginning and many aspects are not resolved. This includes in particular the structure and conformation of polymers at an interface as well as the modification of polymer dynamics by the interface. We have given several examples of the potential of surface and interface analytical techniques. They provide information on surface roughness, surface composition, lateral structure, depth profiles, surface-induced order and interfacial mixing of polymers on a molecular and sometimes subnanometer scale. They thus offer a large variety of possible surface and interface studies which will help in the understanding of polymer structure and dynamics as it is modified by the influence... 

TOF-SIMS can be applied to identify a variety of molecular fragments, originating from various molecular surface contaminations. It also can be used to determine metal trace concentrations at the surface. The use of an additional high current sputter ion source allows the fast erosion of the sample. By continuously probing the surface composition at the actual crater bottom by the analytical primary ion beam, multi element depth profiles in well defined surface areas can be determined. TOF-SIMS has become an indispensable analytical technique in modem microelectronics, in particular for elemental and molecular surface mapping and for multielement shallow depth profiling. 

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.

CPAA may be employed to determine trace element concentrations in bulk solid material, but its importance in our present context is that it permits the characterization of a thin surface layer, i.e. the mass of the analyte element per surface unit, with a good detection limit and outstanding accuracy. For example the composition of a surface layer (or foil) of known thickness can be determined, or, conversely, the thickness of a surface layer of known concentration. Depth profiling or scanning is not possible, and a disadvantage of the method is that heating occurs during irradiation. It is also not possible to discriminate between different oxidation states of the analyte element or between different compounds. 

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. 

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