A method and system are presented for use in measuring one or more characteristics of patterned structures. The method comprises: performing measurements on a patterned structure by illuminating the structure with exciting light to cause Raman scattering of one or more excited regions of the pattern structure, while applying a controlled change of at least temperature condition of the patterned structure, and detecting the Raman scattering, and generating corresponding measured data indicative of a temperature dependence of the detected Raman scattering; and analyzing the measured data and generating data indicative of spatial profile of one or more properties of the patterned structure.