We present a method that allows detailed analysis of complicated spectral e
llipsometry spectra, such as those of thick (approximate to 10 mu m) multil
ayer structures found in modern integrated optics devices. Ellipsometry sho
uld be the natural choice for thorough nondestructive characterisation of t
hose heterostructures, but extraction of the required parameters is often i
mpracticable by common approaches. Our method is based on spline parametris
ations of the unknown optical functions and is applicable to materials eith
er with a smooth optical response or displaying sharp electronic transition
s in the analysed energy range. We illustrate the method with results obtai
ned on thick waveguide structures used for chemical sensors.