An apparatus and method for accurately analyzing transition metal such as iron and copper contained as impurities in a hafnium-containing film on a semiconductor substrate, which is a sample, is provided. Ir-L.alpha. rays selected and split by a monochromator from X rays generated from an X-ray tube having an anode containing iridium, is applied to the sample so as to totally reflect on a hafnium film of the sample, and the fluorescent X rays generated in a direction other than the total reflection direction are detected by a detector. This makes it possible not only to detect Fe--K.alpha. rays, but also to suppress generation of Hf-L.alpha. rays which interferes with detection of Cu--K rays, and to shift the upper limit energy of the Raman scattering to be small so as to cancel overlapping with Cu--K rays.