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.

Effective dielectric properties of Cement/Ba0.06(Na0.5Bi0.5)0.94TiO3 composites: A comparative approach

Lead-free ceramic powder of a morphotropic phase boundary composition Ba0.06(Na0.5Bi0.5)0.94TiO3 (BNBT) was prepared from a solid-state synthesis route. The cement-ceramic (1−ϕ)cement/ϕBNBT; 0 ≤ ϕ 1.0 composites were fabricated. The filler concentration-dependent values of the bulk density and real part of complex permittivity showed an increasing trend of variation while the apparent porosity and imaginary part of complex permittivity followed a decreasing trend. In order to test the acceptability of dielectric mixture equations of the inclusion material in the mixture, five such equations have been chosen. The Bruggeman, and Rother-Lichtenecker equations showed their coherence with minimal deviation from the experimental results of the real part of complex permittivity for the entire measurement range of volume fractions. Also, a first-order exponential growth/decay type of mathematical model was suggested which could fit the experimental data excellently well (r2 > 0.97).

Revealing phase boundaries by weighted parametric structural refinement

Parametric Rietveld refinement from powder diffraction data has been utilized in a variety of situations to understand structural phase transitions of materials in situ. However, when analysing data from lower-resolution two-dimensional detectors or from samples with overlapping Bragg peaks, such transitions become difficult to observe. In this study, a weighted parametric method is demonstrated whereby the scale factor is restrained via an inverse tan function, making the phase boundary composition a refinable parameter. This is demonstrated using compositionally graded samples within the lead-free piezoelectric (BiFeO3) x (Bi0.5K0.5TiO3) y (Bi0.5Na0.5TiO3)1–x–y and (Bi0.5Na0.5TiO3) x (BaTiO3)1–x systems. This has proven to be an effective method for diffraction experiments with relatively low resolution, weak peak splitting or compositionally complex multiphase samples.