Nb₂O₅, LiNbO₃, and (Na, K)NbO₃ Thin Films from High-Concentration Aqueous Nb-Polyoxometalates

Abstract

Synthesizing functional materials from water contributes to a sustainable energy future. On the atomic level, water drives complex metal hydrolysis/condensation/speciation, acid-base, ion pairing, and solvation reactions that ultimately direct material assembly pathways. Here, we demonstrate the importance of Nb-polyoxometalate (Nb-POM) speciation in enabling deposition of Nb₂O₅, LiNbO₃, and (Na, K)NbO₃ (KNN) from high-concentration solutions, up to 2.5 M Nb for Nb₂O₅ and ∼1 M Nb for LiNbO₃ and KNN. Deposition of KNN from 1 M Nb concentration represents a potentially important advancment in lead-free piezoelectrics, an application that requires thick films. Solution characterization via small-angle X-ray scattering and Raman spectroscopy described the speciation for all precursor solutions as the [H_<i>x</i>Nb₂₄O₇₂]^{(<i>x</i>-24)} POM, as did total pair distribution function analyses of X-ray scattering of amorphous gels prior to conversion to oxides. The tendency of the Nb₂₄-POM to form extended networks without crystallization leads to conformal and well-adhered films. The films were characterized by X-ray diffraction, atomic force microscopy, scanning electron microscopy, ellipsometry, and X-ray photoelectron spectroscopy. As a strategy to convert aqueous deposition solutions from {Nb₁₀}-POMs to {Nb₂₄}-POMs, we devised a general procedure to produce doped Nb₂O₅ thin films including Ca, Ag, and Cu doping.