Evaluating the impact of ZnO doping on electrical and thermal properties of calcium-aluminosilicate oxynitride glass-ceramics

This study aimed to investigate the impact of ZnO content on the structure, thermal, and electrical properties of oxynitride glass-ceramic(s) within the Ca–Al–Si–O–N (CASON) system. The base glass had the composition of Ca₇Al₁₄Si₁₇O₅₂N₇, with ZnO additions ranging from 3 to 15 % by weight. A pristine Ca₇Al₁₄Si₁₇O₅₂N₇ glass was successfully prepared by melt-quenching technique followed by converted into glass-ceramic by incorporating various amounts of ZnO using the field-assisted sintering technique. XRD and FESEM analysis confirmed that increasing the amount of Zn increases the crystallinity in the glass matrix. The observed crystalline phases were formed mostly from ZnO and showed higher conductivity than the remaining dielectric matrix. IR spectra confirmed the presence of bands correlated with the presence of Zn and suggested the progressive depolymerization of the silicate-aluminate network as a consequence of increasing Zn content. Density values varied between 2.75 and 2.94 gcm⁻³ and increased with increasing the Zn content in the glass-ceramic. The thermal expansion and thermal conductivity values increased and decreased, respectively, with the increase of Zn content in the matrix. The electrical properties of the samples were investigated using impedance spectroscopy over a wide range of frequencies (10 mHz to 1 MHz) and temperatures (153 K–623 K). The results showed that in the glass without ZnO and glass-ceramic(s) with a small addition of ZnO, the conductivity is mainly dominated by the transfer of oxygen ions and, to a small extent, by the presence of electronic conductivity. As the ZnO content increases, continuous conduction paths are formed between the ZnO crystallites, and the electrical conductivity increases rapidly and becomes dominated by electron transfer.