The ability of a Modulated Optical Reflectivity (MOR) or Thermal Wave (TW) system to measure characteristics of a sample based on the amplitude and phase of a probe beam reflected from the surface of the sample can be improved by providing a polychromatic pump and/or probe beam that can be scanned over a wide spectral range, such as a range of at least 100 nm. The information contained in the spectral dependencies of a TW response obtained from the sample can be compared and/or fitted to corresponding theoretical dependencies in order to obtain more precise and reliable information about the properties of the particular sample than is available for single-wavelength systems. This information can further be combined with measurements taken for varying spot separations or varying pump source modulation frequency, as well as with photo-thermal radiometry (PTR), spectroscopic reflectometry, and/or ellipsometry measurements.