PVA/CuI polymer composite samples have been prepared and subjected to characterizations using FT-IR spectroscopy, DSC analysis, ac spectroscopy and dc conduction. The FT-IR spectral analysis shows remarkable variation of the absorption peak positions whereas DSC illustrates a little decrease of both glass transition temperature, Tg, and crystallization fraction, χ, with increasing CuI concentration. An increase of dc conductivity for PVA/CuI nano composite by increasing CuI concentration is recoded up to 15 wt%, besides it obeys Arhenuis plot with an activation energy in the range 0.54–1.32 eV. The frequency dependence of ac conductivity showed power law with an exponent 0.33 < s < 0.69 which predicts hopping conduction mechanism. The frequency dependence of both dielectric permittivity and dielectric loss obeys Debye dispersion relations in wide range of temperatures and frequency. Significant values of dipole relaxation time obtained which are thermally activated with activation energies in the range 0.33–0.87 eV. A significant value of hopping distance in the range 3.4–1.2 nm is estimated in agreement with the value of Bohr radius of the exciton.
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