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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-κ 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., WMα, Cr Kα) for the low Z elements such as Na, Mg, and Al, a moderate-energy excitation (10-20 keV, e.g., WLβ, MoKα) 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 1010-1011 at/cm2 can be achieved, even for novel contaminants and substrates. As the International Technology Roadmap for Semiconductors (ITRS) requires control below 5×109 at/cm2, 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. [ABSTRACT FROM PUBLISHER]

The experimental study of the bonding geometry of a (100)Ge surface exposed to H2S in the gas phase at 330 °C shows that 1 ML S coverage with (2×1) surface reconstruction can be achieved. The amount of S on the Ge surface and the observed surface periodicity can be explained by the formation of disulfide bridges between Ge–Ge dimers on the surface. First-principles molecular dynamics simulations confirm the preserved (2×1) reconstruction after dissociative adsorption of H2S molecules on a (100)Ge (2×1) surface, and predict the formation of (S–H)–(S–H) inter-Ge dimer bridges, i.e., disulfide bridges interacting via hydrogen bonding. The computed energy band gap of this atomic configuration is shown to be free of surface states, a very important finding for the potential application of Ge in future high performance integrated circuits. [ABSTRACT FROM AUTHOR]

In future microelectronic devices, SiO2 as a gate dielectric material will be replaced by materials with a higher dielectric constant. One such candidate material is HfO2. Thin layers are typically deposited from ligand-containing precursors in chemical vapor deposition (CVD) processes. In the atomic layer deposition (ALD) of HfO2, these precursors are often HfCl4 and H2O. Obviously, the material properties of the deposited films will be affected by residual ligands from the precursors. In this paper, we evaluate the use of grazing incidence--and total reflection-X-ray fluorescence spectrometry (GI-XRF and TXRF) for Cl trace analysis in nanometer-thin HfO2 films deposited using ALD. First, the results from different X-ray analysis approaches for the determination of Hf coverage are compared with the results from Rutherford backscattering spectrometry (RBS). Next, we discuss the selection of an appropriate X-ray excitation source for the analysis of traces within the high-kappa: layers. Finally, we combine both in a study on the accuracy of Cl determinations in HfO2 layers.