We report on the application of synchrotron radiation based high-resolution grazing-emission x-ray fluorescence ͑GEXRF͒ method to measure low-level impurities on silicon wafers. The presented high-resolution GEXRF technique leads to direct detection limits of about 10 12 atoms/ cm 2 . The latter can be presumably further improved down to 10 7 atoms/ cm 2 by combining the synchrotron radiation-based GEXRF method with the vapor phase decomposition preconcentration technique. The capability of the high-resolution GEXRF method to perform surface-sensitive elemental mappings with a lateral resolution of several tens of micrometers was probed.The production of ultraclean silicon wafers is one of the most important issues for Si-based microelectronics technology. According to the International Technology Roadmap for Semiconductors ͑ITRS͒ ͑Ref. 1͒, a sensitivity below the level of 10 9 atoms/ cm 2 for transition metals on Si wafer surfaces is needed. At present, the total reflection x-ray fluorescence ͑TXRF͒ method 2-5 combined with intense synchrotron radiation ͑SR͒ sources offers the best possibilities for measuring very low concentration of impurities on Si surfaces. Using SR beams, a sensitivity level of 10 8 atoms/ cm 2 for direct detection of Cu was achieved. 6 On the other hand, in the case of low Z impurities, such as Al, the achieved detection limits ͑DLs͒ by means of the SR-TXRF technique are still above the ITRS requirements. 1,7,8 Moreover, the SR-based TXRF technique, which employs the grazing incidence geometry, cannot benefit from the available microfocused x-ray beams at synchrotrons in order to perform high-spatial resolution two-dimensional ͑2D͒ surfaces mapping. Therefore, further development of new direct techniques to measure metallic impurities on Si wafers is still a challenging problem. In this context, the application of the SR based grazing-emission x-ray fluorescence ͑GEXRF͒ technique for measuring x-ray emission from Si-wafer impurities can be regarded as a good alternative. In the GEXRF technique, which is a kind of inverse of TXRF, the excited x-ray fluorescence is observed at grazing emission angles exit smaller than the critical angle c . 9-12 Such a geometry results in a relative enhancement of the characteristic fluorescence emission from the surface with respect to the substantially decreased fluorescence signal from the bulk substrate.In this paper, we report on a high-resolution GEXRF technique developed for the detection of low-level impurities on Si surfaces. In this method the grazing emission geometry is combined with a wavelength-dispersive spectrometer. The measurements were performed at the European Synchrotron Radiation Facility ͑ESRF͒ in Grenoble, France, at the beamline ID21, employing a von Hamos-type crystal spectrometer 13 for the high-resolution detection of the fluorescence x rays from the impurities deposited on Si wafers. As for small grazing emission angles exit , the photon beam spot on the target, observed in the direction defined by the Bragg angle Bragg , appear...