Synthesis, characterization and DFT raman study of pure and Mn‐doped LiTaO ₃ nanofibers

Pure and Mn-doped lithium tantalate nanofibers, with Mn concentrations of 1%, 2.5%, and 5%, were synthesized by the electrospinning method. The morphology, microstructure, and crystal structure of as-spun and annealed composite nanofibers were characterized by scanning electron microscopy, X-ray diffraction, and transmission electron microscopy. Raman spectroscopy has shown to be a powerful tool to detect either local variations or changes of the whole structure. Position and width of one Raman line can be used as markers of a structural change. Some vibrational modes are especially associated with the site of Li or Ta ions and so, they can be affected by the introduction of dopant ions. Any damages or local changes in the microstructure can be detected by a line broadening. With the use of Raman spectroscopy, the sites where Mn ions enter the doped structures were established by recording the shift and broadening of peaks in Mn-doped structures with respect to pure lithium tantalate. Thus it was proven that Mn ions enter the Li sites for low Mn concentration and, on the other hand, for higher concentrations, the dopant substitutes Li and Ta sites. First-principles calculations were performed within the density functional theory, including lattice-dynamic calculations of the phonon modes at the zone center (Γ point), for the pure structure, to find the irreducible representation of the modes.