Synthesis, Thermal Evolution and Optical Properties of Eu-Doped Lanthanum Hydroxycarbonates and Oxycarbonates

Rare-earth hydroxycarbonates and oxycarbonates are attractive functional materials because their crystal chemistry and optical response can be tailored through controlled cation substitution. In this work, Eu-doped lanthanum hydroxycarbonates with nominal europium contents of 1, 3, and 5 mol% were synthesized by combining co-precipitation and hydrothermal treatment at 140 °C for 24 h and subsequently calcined at 500 °C for 0.5 h to obtain the corresponding oxycarbonates. X-ray diffraction showed that the as-synthesized powders consist of single-phase hexagonal LaCO3OH, while the calcined products are single-phase La2O2CO3. In both structural families, systematic peak shifts with increasing Eu content indicated the formation of homogeneous substitutional solid solutions. Thermal analysis revealed a clear two-step decomposition pathway for the hydroxycarbonate precursors, with endothermic events at about 530 and 850 °C, consistent with the sequential transformation from hydroxycarbonate to oxycarbonate and, finally, to oxide. UV-Vis absorption measurements highlighted a dopant-dependent shift in the absorption edge in both hydroxycarbonate and oxycarbonate systems. Kubelka–Munk analysis showed that the estimated band-gap energy increases with Eu content, from 4.9 to 5.4 eV for LaCO3OH-based samples and from 4.7 to 5.1 eV for La2O2CO3-based samples. These results demonstrate that europium incorporation is an effective strategy for tuning the structural evolution and optical properties of lanthanum carbonate-derived materials, thus supporting their potential use in UV-responsive rare-earth-based functional systems.