Application of x-ray fluorescence (XRF) analysis for detection of low-level impurities in materials can be limited by the x-ray resonant Raman scattering (RRS) process. This effect is particularly important for detection of ultra-low concentrations of low-Z impurities in high-Z materials. In this case, the low-energy tail of strong fluorescence line of bulk material forms a "background" for detection of low-energy x-rays from the impurities. By tuning the primary x-ray beam energy below the absorption the strong x-ray fluorescence of bulk material can be eliminated, but instead, the x-ray Resonant Raman Scattering (RRS) structure appears limiting thus a sensitivity of the x-ray fluorescence technique for detection of low-Z impurities in the studied sample. Well known example of this effect is a problem of detection of ultra-low concentrations of Al on the surface of Si-wafers, which have to be controlled below 1E10 atoms/cm2 level for future silicon-based microelectronic technology. It was demonstrated that in this particular case the resonant Raman scattering process limits a sensitivity of the total-reflection x-ray fluorescence (TXRF) technique [1] for detection of aluminum contamination on Si–wafer. In fact, in the TXRF method which uses semiconductor detectors, having energy resolution well above 100 eV, the Al-Kα fluorescence line is overlapping with RRS structure appearing for photon beam energies tuned below the Si-K-shell absorption edge to avoid an intense Si-Kα fluorescence. Consequently, the TXRF limits for detection of Al on Si surface are about 1E12 atoms/cm2 for optimized synchrotron radiation excitation conditions. Due to this limitation the TXRF method is usually combined with the vapor phase decomposition (VPD) technique enhancing by 2-3 orders of magnitude a sensitivity for detection of Al on Si-wafers. In order to investigate new alternatives for detection of Al in silicon we have measured [2] with high-resolution the RRS spectra for Si and SiO 2 below the Si K-shell edge at the ESRF at beamline ID21. The high-resolution measurements were performed using a von Hamos Bragg-type curved crystal spectrometer [3]. In these measurements, which were performed at different photon beam energies tuned below the Si-K absorption edge, the x-ray RRS spectra were measured for the first time and the total x-ray cross sections for the at the 1s2p RRS process in Si and SiO2 were obtained. In general, the experimental RRS cross sections are well described by the theoretical calculations based on the Kramers-Heisenberg approach. We have also demonstrated that from the measured RRS x-ray spectra the density of unoccupied states in silicon can be derived, giving thus similar information as one obtained by using the x-ray absorption techniques. Guided by the results obtained for the RRS in silicon we have proposed to measure the ultra low level Al impurities on Si by using the high-resolution grazing emission x-ray fluorescence (GEXRF) technique, which is an "inverse" TXRF method. The results demonstrate that the high-resolution GEXRF method can be successfully applied for detection of low-level Al impurities in silicon. However, the further aspects of application of a high-resolution synchrotron radiation based GEXRF technique in material science will be discussed separately.