X-ray, micro-Raman, optical absorption/emission studies of ErNbO ₄ grown by vapor transport equilibration

Vapor transport equilibration (VTE) treatments were performed on a Y-cut bulk Er (1.6 mol%)-doped congruent LiNbO₃ crystal and an X-cut pure congruent crystal, on one surface of which a 40 nm-thick film of erbium metal was coated before the VTE treatment. Scanning electron microscope, powder or single-crystal X-ray diffraction (XRD), polarized infrared absorption/emission of Er³⁺ as well as micro-Raman spectroscopy were used to study the two VTE crystals. The results are discussed in comparison with a corresponding as-grown bulk Er-doped crystal, calcined ErNbO₄ powder, and a locally Er-doped congruent LiNbO₃ crystal prepared by using the standard Er-diffusion technique. The experimental results show that the VTE treatment induces the formation of micrometer-sized ErNbO₄ precipitates with the crystallographic morphology of a flat polyhedron not only on the surfaces of both crystals but also in the bulk of the homogeneously Er-doped one. The optical absorption and emission studies show that the formation of the precipitates results in substantial spectral changes in both the 0.98 and 1.5 μm regions. The micro-Raman studies allow to resolve four additional Raman peaks around 800 cm^-1 in the E(TO) spectra of the two VTE crystals. These additional Raman peaks are associated with the characteristic vibrations with respect to the NbO₄^3- group. Characteristic XRD, optical absorption, and emission and Raman peaks for identifying the ErNbO ₄ phase are proposed. Finally, the formation mechanism and light-scattering effect of the precipitates are discussed.