In this paper, a number of case studies on the analysis of novel metallic contaminants on conventional and alternative substrates using the technique of total reflection X-ray fluorescence spectrometry (TXRF) is presented. Investigated materials include Si and Ge substrates, high-kappa dielectric contaminants, and layers, and Si wafers contaminated with elements from metal gates and Cu interconnects. One focus is on the application and optimization of detection limits in direct TXRF. For the TXRF analysis of contaminants on Si wafers, a general conclusion is that a combination of three excitation sources is needed to cover the whole range of interest: a low-energy excitation (about 5 keV, e.g., W M alpha, Cr K alpha) for the low Z elements such as Na, Mg, and Al, a moderate-energy excitation (10-20 keV, e.g., W L beta, Mo K alpha) for the 3d-transition elements, and a high-energy excitation (25-35 keV, e.g., W, continuum) for the analysis of elements such as Zr, Ru, Mo, and Pd. Also, for the analysis of novel substrates using direct TXRF, a careful selection of the excitation source results in better detection limits. In this way, detection limits at 10(10)-10(11) at/cm(2) can be achieved, even for novel contaminants and substrates. As the International Technology Roadmap for Semiconductors (ITRS) requires control below 5 x 109 at/cm(2), the application of a preconcentration procedure such as vapor phase decomposition-droplet collection TXRF (VPD-DC-TXRF) is required. Proper use of this procedure allows the improvement of the detection limits by two to three orders of magnitude, depending on wafer size and chemical collection efficiency. The usability of this preconcentration procedure in combination with TXRF will be demonstrated for noble elements and germanium substrates.
