Hydrothermal Synthesis of LaCO3OH and Ln3+-doped LaCO3OH Powders under Ambient Pressure and Their Transformation to La2O2CO3 and La2O3

Orthorhombic and hexagonal lanthanum(III) hydroxycarbonate ($LaCO_3OH$) and $Ln^{3+}$-doped $LaCO_3OH$ ($LaCO_3OH:Ln^{3+}$, where Ln = Ce, Eu, Tb, and Ho) powders were prepared by a hydrothermal reaction under ambient pressure and characterized by thermogravimetry, powder X-ray diffraction, infrared and luminescence spectroscopy, and field-emission scanning electron microscopy. The polymorph of $LaCO_3OH$ depended on the reaction temperature, inorganic salt additive, species of $Ln^{3+}$ dopant, and solvent. The calcination of orthorhombic $LaCO_3OH:Ln^{3+}$ (2 mol %) powers at $600^{\circ}C$ yielded a mixture of hexagonal and monoclinic $La_2O_2CO_3:Ln^{3+}$ powders. The relative quantity of the latter increased with decreasing ionic radius of the $Ln^{3+}$ dopant ion and increasing doping concentrations. On the other hand, the calcination of hexagonal $LaCO_3OH:Ln^{3+}$ (2 mol %) powders at $600^{\circ}C$ resulted in a pure hexagonal $La_2O_2CO_3:Ln^{3+}$ powder, regardless of the species of $Ln^{3+}$ ions (Ln = Ce, Eu, and Tb). The luminescence spectra of $LaCO_3OH:Ln^{3+}$ and $La_2O_2CO_3:Ln^{3+}$ were measured to examine the effect of their polymorph on the spectra.