Growth of tungsten bronze phase out of niobate perovskite phase for opto-ferroelectric applications

Engineering the optical bandgaps of classic ferroelectrics from the typical ultraviolet range down to the visible range is an emerging methodology of developing the next-generation optoelectric and opto-ferroelectric devices including ferroelectric solar cells light-driven transistors and modulators and multi-sensors/energy harvesters. Recently a material interface comprised of a pseudo-morphotropic phase boundary between the tungsten bronze and perovskite phases of the KNBNNO [(K,Na,Ba)_x(Ni,Nb)_yO_z] has been reported to be an effective approach for bandgap engineering while retaining excellent ferroelectricity and piezoelectricity of the perovskite-phased KNBNNO. However this approach requires the compositions of the materials to be determined at the synthesis stage leaving little room for any further modification of the microstructure and functional properties at the post-processing stage. This paper presents a post-processing method that is atmospheric annealing in N₂ and O₂ to grow the necessary tungsten bronze phase out of the perovskite phase in the KNBNNO. This method is advantageous over the previously reported because it enables to grow the tungsten bronze–perovskite interface region independent of the initial composition. The distinctive electrical properties and the giant tunability of photoconductivity of the tungsten bronze phase the perovskite phase and the interface are characterized in detail in this paper supporting the exploitation of fabricating opto-ferroelectric devices using the reported method which is compatible and comparable with some of the post-processing methods applied in the silicon industry.