Piezoelectric Nanogenerators based on Lead Zirconate Titanate nanostructures: An insight into the effect of potential barrier and morphology on the output power generation

The high internal resistance of the perovskite materials used in Nanogenerators (NGs) lowers the power generation. It severely restricts their application for mechanical energy harvesting from the ambient source. In this work, we demonstrate a flexible Piezoelectric NG (PENG) with an improved device structure. Hydrothermally grown one-dimensional Lead Zirconate Titanate (Pb(ZrTi)O3) of different morphologies are used as the generating material. The morphology of the PZT nanostructures, engineered from nanoparticles to needle-shaped nanowires to increase the surface to volume ratio, provides effective mechanical contact with the electrode. The reduction of the internal resistance of the PENG has been achieved by two ways: i) fabrication of interdigitated electrodes (IDE) to increase the interfacial polarization and ii) lowering of Schottky barrier height (SBH) at the junction of the PZT nanostructure and the metal electrode by varying the electrode materials of different work functions. We find that lowering of the SBH at the interface contributes to an increased piezo voltage generation. The flexible nano needles-based PENG can deliver output voltage 9.5 V and power density 615 μW/cm2 on application low mechanical pressure (~1 kPa) by tapping motion. The internal resistance of the device is ~0.65 MΩ. It can charge a 35 μF super-capacitor up to 5 V within 20 s. This study provides a systematic pathway to solve the bottlenecks in the piezoelectric nanogenerators due to the high internal resistance.

STRUCTURE CHANGING OF SUBMICRON PZT FILMS WITH A FINE VARIATION OF THE COMPOSITION CORRESPONDING TO MORPHOTROPIC PHASE BOUNDARY

В работе обсуждаются возможности тонкого варьирования состава субмикронных сегнетоэлектрических пленок твердых растворов цирконата-титаната свинца, соответствующих области морфотропной фазовой границы. Варьирование состава осуществлялось путем изменения расстояния от мишени до подложки в диапазоне 30 - 70 мм в установке высокочастотного магнетронного распыления керамической мишени при осаждении пленок на «холодную» подложку платинированного кремния. Это позволило изменять состав осаждаемых пленок (т.е., элементное соотношение атомов Zr и Ti) в диапазоне 0 -1,5% при сохранении однофазности сформированных перовскитовых пленок в процессе отжига при 580°C. При этом пленки характеризовались элементной неоднородностью состава по толщине, достигающей нескольких процентов. Толщина тонких слоев цирконата-титаната свинца составляла 500 нм. Исследовались изменения микроструктуры и параметров кристаллической решетки. Изменения состава пленок сопровождались существенными изменениями характера сферолитовой микроструктуры и ростовой текстуры. Был обнаружен резкий скачок квазикубического параметра кристаллической решетки, причиной которого может являться фазовая трансформация сегнетоэлектрической фазы - от ромбоэдрической модификации к двухфазному состоянию, предположительно состоящему из моноклинной и тетрагональной модификаций. The paper discusses the possibility of a fine variation in the composition of submicron ferroelectric films of lead zirconate titanate solid solutions corresponding to a morphotropic phase boundary. Composition was varied by changing the distance from the target to the substrate in the range of 30 - 70 mm in an installation for radio-frequency magnetron sputtering of a ceramic target, in which films deposition occurred on a «cold» platinized silicon substrate. This made it possible to change the composition of the deposited films (i.e., the elemental ratio of Zr and Ti atoms) in the range of 0 - 1,5% while maintaining the single-phase perovskite films annealed at 580 °С. In this case, the films were characterized by elemental inhomogeneity of the composition over the thickness, reaching several percents. The thickness of thin lead zirconate titanate layers was 500 nm. Changes in the microstructure and crystal lattice parameters were studied. The change in the composition of the films was accompanied by significant changes in the nature of the spherulite microstructure and growth texture. A sharp jump in the quasi-cubic crystal lattice parameter was discovered, which may be caused by the phase transformation of the ferroelectric phase - from the rhombohedral modification to the two-phase state, presumably consisting of monoclinic and tetragonal modifications.