Crystal structure and compositional analysis of epitaxial (K sub(0.56)Na sub(0.44))NbO sub(3) films prepared by hydrothermal method

(K sub(x)Na sub(1-x))NbO sub(3) films were deposited on Nb-doped (100)SrTiO sub(3) substrates at 240 degree C for times between 1 and 6 h by a hydrothermal method. Over this time series, the measured (K + Na)/Nb ratio of the films was found to remain constant, but the bulk K/(K + Na) ratio, x, decreased from an initial value of 0.75-0.56. It was determined that film growth initially proceeded through crystallization of the K-rich phase (K sub(0.75)Na sub(0.25))NbO sub(3). For film growth times greater than 3 h, a second perovskite phase with a smaller unit cell volume was detected, with an estimated composition of (K sub(0.36)Na sub(0.64))NbO sub(3). As such, the measured bulk composition value x = 0.56 was determined to be the result of a combination of these two phases, as opposed to originating from a single phase. Cross-sectional transmission electron microscopy analyses of films prepared for 6 h revealed that they consist of two layers in the direction normal to the substrate; this bilayer-type structure, only observed for hydrothermal growth of this material, is considered to arise from the large solubility mismatch between the Nb precursor and KOH and NaOH in the growth solution.