A Comprehensive Study of Ca9Tb({PO}4)7 and Ca9Ho({PO}4)7 Doped beta-Tricalcium Phosphates: Ab initio Crystal Structure Solution, Rietveld Analysis, and Dielectric Properties

The scientific interest toward the structural, luminescence, and dielectric properties of tricalcium phosphate (TCP) materials, in particular, the doped TCP-based compounds, is mainly due to their biocompatibility and bioactivity behavior and the increasing number of their applications. In the literature, structural investigations of a doped beta-TCP compound are usually carried out by powder diffraction data under the assumption that it has a centrosymmetric whitlockite structure. Recent studies have shown that this assumption is not always fulfilled. For this reason, it is necessary to use methods of nonlinear and dielectric spectroscopy to prove the true symmetry of whitlockite-like phases. This work provides a detailed and comprehensive study on the structural, dielectric, and nonlinear properties of the polycrystalline Tb- and Ho-doped tricalcium phosphates, chemically Ca9Tb(PO4)(7) and Ca9Ho(PO4)(7). Their crystal structure was explored using powder X-ray diffraction, adopting an ab initio approach for the structure solution followed by the Rietveld refinement. For Ca9Tb(PO4)(7), the qualitative analysis of the experimental powder X-ray diffraction pattern revealed that the sample was not a single phase. Nevertheless, its crystal structure has been determined by Direct Methods. The presence of the dopant cation was omitted in the solution process by Direct Methods and considered in the successive Rietveld refinement step. The analysis of the occupancies has clarified the Tb3+ cation distribution in its preferential sites. The same pathway has been followed for the Ca9Ho(PO4)(7) sample, which corresponded to a single-phase structure. The dielectric properties of the two doped compounds (Tb3+ and Ho3+) were also examined, and reversible ferroelectric-paraelectric phase transitions were found at 862 and 872 K, respectively.