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

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 similar to 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 [HxNb24O72]((x-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 Nb-24-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 {Nb-10}-POMs to {Nb-24}-POMs, we devised a general procedure to produce doped Nb3O5 thin films including Ca, Ag, and Cu doping.