Semiconducting Na2O-V2O5-TeO2 glasses with various Na2O contents were melted and subjected to controlled heating to improve conductivity. Topography analysis were performed using confocal microscopy and scanning electron microscopy on both as-quenched and heat-treated samples. X-ray diffraction confirmed the amorphous nature of the samples post-melting, with subsequent heating resulting in the formation of nanocrystallites primarily composed of vanadium ions. The Na2O addition caused progressive depolymerization of the tellurite-vanadate network, as evidenced by IR spectroscopy, although heating exhibited an opposing effect, particularly noticeable in vanadate-related bands. Thermal properties revealing a decrease in the glass transition temperature, crystallization process, and thermal stability with increasing sodium ion concentration. Electrical properties were investigated using impedance spectroscopy, which enabled determination of DC conductivity values, polaron jump energies, and disturbance energies in the samples. The electrical conductivity mechanisms were described as mixed ionic-polaronic, with polaron hopping predominating. Heat treatment significantly enhanced polaron conductivity and altered its nature.
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