Crystallization and phase transition boosted optical linear& nonlinear and magnetic properties in transparent xCu: BaSnO3 NCs/glass-ceramic

Abstract

In this study, cubic xCu: BaSnO₃ (x = 0, 1, 3, and 5 mol%) perovskite nanocrystals were synthesized using a hydrothermal method. The influence of Cu doping levels on the crystal structure, morphology, size, and properties was analyzed using X-ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FT-IR), Raman, Ultraviolet-Visible Spectroscopy (UV–vis), Vibrating Sample Magnetometry (VSM), and X-ray Photoelectron Spectroscopy (XPS) techniques. Across the 1–5 % doping range, the cubic BaSnO₃ structure was maintained with Cu²⁺ in CuO₆ replacing Sn⁴⁺ in the B-site. XPS analysis confirmed the formation of oxygen vacancies due to charge imbalance, leading to a decrease in optical bandgap and an increase in ferromagnetic moment. When various contents of xCu: BaSnO₃ were doped into borosilicate glass, significant impacts on the glass network, crystallization, and properties were observed. Nanocrystals (∼50 nm) transitioned from cubic to orthorhombic phase beyond 3 mol% doping, modifying the glass network by converting BO₃ to BO₄, AlO₄ to AlO₆, and CuO₆ to CuO₄. This phase change endowed the glass's strong ferromagnetic moment and absorption due to the t_2 g→e_g transitions of Cu²⁺ in CuO₆, and reduced the optical bandgap from 3.16 to 2.2 eV. The glass also exhibited improved Vickers hardness (475 HV) and a high Verdet constant of 0.174 min/G·cm due to network modifications. Glass also shows a distinct red emission at 596 nm with a 160 µs lifetime and good thermal stability, while doping levels above 3 % resulted in emission quenching. The optical nonlinear absorption coefficient and nonlinear susceptibility increased with higher doping levels, reaching huge values of α₃: 5.12×10⁻¹⁰ m/W and χ⁽³⁾: 7.52×10⁻¹⁰ esu, indicating potential for self-focusing applications. The increased polarizability also resulted in a high dielectric constant (18) and a large P-E loop of glasses which are promising for advanced photonics devices.