Agilent Technologies has some nice material measurement instrumentation. I think you can search for Agilent Technologies application notes for the same.
in the past we have worked with the characterization of a two layer substrate in the frequency range 0-40 GHz. We used a coplanar waveguide (CPW) transmission line. You can find the description of our method in the paper
"Dielectric Permittivity of Porous Si for Use as Substrate Material in Si-Integrated RF Devices"
You can also obtain a more general view on this field from the book :
"Microwave Electronics: Measurement and Materials Characterization" of L. F. Chen, C. K. Ong, C. P. Neo, V. V. Varadan, V. K. Varadan