Elemental sensitivity

Wavelength, nm Element Sensitivity Wavelength, nm Element Sensitivity... 

This E is characteristic for each energy level ia the element and can be used to determine the element from which the electron origiaated. Differences ia E form the basis of elemental sensitivity ia xps. 

Figure 10 shows a comparison of Scofield s calculated values with experimentally measured values (24) which, in addition to (, are dependent on spectrometer transmission function. The overall agreement between the calculated and experimental values is quite good. The far rightjy-axis in Figure 10 indicates the experimentally accessible surface sensitivities in monolayers (ML) as a function of atomic number. For most elements, sensitivities on the order of 1% of a ML are achievable. 

Elemental sensitivity Scales as the square of nuclear charge best for heavy elements (< 10 monolayer) poor for hydrogen... 

There are three types of instruments that provide STEM imaging and analysis to various degrees the TEM/STEM, in which a TEM instrument is modified to operate in STEM mode the SEM/STEM, which is a SEM instrument with STEM imaging capabilities and dedicated STEM instruments that are built expressly for STEM operation. The STEM modes of TEM/STEM and SEM/STEM instruments provide useful information to supplement the main TEM and SEM modes, but only the dedicated STEM with a field emission electron source can provide the highest resolution and elemental sensitivity. 

Alternatives to XRD include transmission electron microscopy (TEM) and diffraction, Low-Energy and Reflection High-Energy Electron Diffraction (LEED and RHEED), extended X-ray Absorption Fine Structure (EXAFS), and neutron diffraction. LEED and RHEED are limited to surfaces and do not probe the bulk of thin films. The elemental sensitivity in neutron diffraction is quite different from XRD, but neutron sources are much weaker than X-ray sources. Neutrons are, however, sensitive to magnetic moments. If adequately large specimens are available, neutron diffraction is a good alternative for low-Z materials and for materials where the magnetic structure is of interest. 

Reflected Electron Energy-Loss Spectroscopy (REELS) has elemental sensitivities on the order of a few tenths of a percent, phase discrimination at the few-percent level, operator controllable depth resolution from several nm to 0.07 nm, and a lateral resolution as low as 100 nm. 

Electron spectroscopic techniques require vacuums of the order of 10 Pa for their operation. This requirement arises from the extreme surface-specificity of these techniques, mentioned above. With sampling depths of only a few atomic layers, and elemental sensitivities down to 10 atom layers (i. e., one atom of a particular element in 10 other atoms in an atomic layer), the techniques are clearly very sensitive to surface contamination, most of which comes from the residual gases in the vacuum system. According to gas kinetic theory, to have enough time to make a surface-analytical measurement on a surface that has just been prepared or exposed, before contamination from the gas phase interferes, the base pressure should be 10 Pa or lower, that is, in the region of ultrahigh vacuum (UHV). 

The element sensitivity is determined by the ionization probability of the sputtered atoms. This probability is influenced by the chemical state of the surface. As mentioned above, Cs" or OJ ions are used for sample bombardment in dynamic SIMS, because they the increase ionization probability. This is the so-called chemical enhancement effect. 

The advantages of SIMS are its high sensitivity (detection limit of ppms for certain elements), its ability to detect hydrogen and the emission of molecular fragments that often bear tractable relationships with the parent structure on the surface. Disadvantages are that secondary ion formation is a poorly understood phenomenon and that quantification is often difficult. A major drawback is the matrix effect secondary ion yields of one element can vary tremendously with chemical environment. This matrix effect and the elemental sensitivity variation of five orders of magmtude across the periodic table make quantitative interpretation of SIMS spectra oftechmcal catalysts extremely difficult. 

INAA is well suited to study homogeneity of small samples because of its dynamic range of elemental sensitivity. The technique allows for the use of small solid samples, with the smallest usable sample size in the range of 0.5 mg to i mg as determined by handling and blank considerations. The INAA analytical procedure is well understood and characterized with mathematical relationships. Its analytical uncertainties can be sufficiently controlled and can be well determined for a particular procedure. This allows the calculation of the contribution of material heterogeneity to the uncertainty budget based on experimental data. 

The mass spectrometer is mainly used as a mass detector in chromatography (GC, SFC, HPLC, SEC, TLC). With the great variety of interfaces, ionisation modes and mass spectrometers, chromatography-mass spectrometry is highly diversified. High-resolution separations combined with accurate mass measurements and element-sensitive detection (MIP, ICP) have been reported. 

The matrix is the major component of the solution (or of the solid if using laser ablation or SEM). Matrix differences between standards and samples or between samples may result in differences of elemental sensitivity. Therefore, it is desirable that all the blanks, calibration standards, and samples have the same matrix (i.e., are matrix matched). This is relatively easy to achieve in solution, but can be a major problem with the analysis of solid samples. 

The highest element sensitivity (see also Figure 6.12) is observed for the heavy radionuclide elements Th and U. In general, a similar dependence is found for RSCs from masses under optimized experimental conditions in LA-ICP-MS and ICP-MS using the ICP-QMS Elan 6000. 

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