Tetragonal tungsten bronze phase thin films in the K–Na–Nb–O system: Pulsed laser deposition, structural and dielectric characterizations

Abstract

Pulsed laser deposition parameters have been determined to synthesize pure Tetragonal Tungsten Bronze (TTB) phase thin films in the (K,Na)–Nb–O system (KNN). In relation to the high volatility of alkaline elements, it was found that the target composition and the target-substrate distance are of first importance. The TTB phase was identified by X-ray and electron diffraction and the surface microstructure consisting mainly of nanorods supports the formation of hallmark of the TTB phase. Poly-oriented nanorods have been obtained on both C-plane sapphire and (111)Pt/TiO2/SiO2/(001)Si substrates whereas horizontal nanorods oriented along the (hk0) planes have been grown on (100) and (110) SrTiO3. All the nanorods are parallel together when grown on (110) SrTiO3 and they present two in-plane orientations rotated of 90° from each other on (100) SrTiO3. Dielectric characteristics (dielectric permittivity εr, and loss tangent tanδ) have been measured at low (1 kHz - 1 MHz) and high (1 GHz–40 GHz) frequencies, on films deposited on Pt coated silicon and sapphire, respectively. A value of εr = 200 at 1 kHz with tanδ = 0.015 were measured in a parallel plate capacitor configuration, whereas εr = 130 and tanδ = 0.20 at 10 GHz were retrieved from transmission lines printed on the KNN TTB thin film grown on C-plane sapphire. Raman investigations of the TTB films were performed in the temperature range 77–873 K, confirming the TTB phase formation and the absence of structural transition. Piezoelectric Force Microscopy measurements evidenced a piezoelectric signal although no switching could be performed. However the dielectric measurements, complicated by high leakage currents when a DC voltage was applied, did not evidence any proof of ferroelectricity for the undoped KNN TTB films whereas results reported on other niobates (A,A′)6Nb10O30 (with A: K, Na and A’: Sr, Ba, Ca) have shown Curie temperatures, lying between 156 °C and 560 °C, separating the paraelectric phase (space group: P4/mbm N°127) and the ferroelectric one (space group: P4bm N°100).