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Title: Synthesis, structural and ferroelectric properties of perovskite-like layered structured materials
Author: Chen, Chen
ISNI:       0000 0004 5370 2444
Awarding Body: Queen Mary, University of London
Current Institution: Queen Mary, University of London
Date of Award: 2015
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Perovskite-like layered structured (PLS) compounds display a range of interesting physical and chemical properties, including photocatalysis, photoluminescence, ion conductivity, electrochemical stability, magnetic properties, ferroelectricity and piezoelectricity. There are mainly three homologous series of PLS compounds distinguished by their different BO6 octahedra orientation: the Dion-Jacobson phase (A'An-1BnO3n+1); the AnBnO3n+2 phase; and the hexagonal phase (AnBn-1O3n). Some of the 4-layer AnBnO3n+2 compounds, like La2Ti2O7 and Sr2Nb2O7, have been reported to be ferroelectrics with super high Curie point (above 1300 °C), but no ferroelectric properties have been reported for the 2-layer and 3-layer AnBnO3n+2 compounds, and also there are few reports on the ferroelectric properties of compounds with Dion-Jacobson structure and hexagonal structure. Consequently, in this work, the crystallographic structures, microstructures, dielectric, ferroelectric and piezoelectric properties of (AxLa1-x)Ti2O7 (A = Sm and Eu) solid solutions with 4-layer AnBnO3n+2 structure, Pr3Ti2TaO11 with 3-layer AnBnO3n+2 structure, LaTaO4 with 2-layer AnBnO3n+2 structure, ABiNb2O7 (A = Rb and Cs) with Dion-Jacobson structure and Sr6TiNb4O18 with hexagonal structure were studied. Spark plasma sintering (SPS) was used to sinter ceramics with high density and preferred orientation. X-ray diffraction refinement (XRD) and transmission electron microscopy (TEM) were used to study the crystallographic structures and microstructures of the layer structured compounds. The ferroelectricity was studied using the current-electric field and polarization-electric field hysteresis loops. The Curie point and phase transitions were studied using the temperature dependence of the dielectric constant and loss. Piezoresponse force microscopy (PFM) was also used to study the ferroelectric domain structure of some layer structured compounds. In the first part of this work, the piezoelectric constant of La2Ti2O7 was improved by doping Sm. The crystallographic structure of (Eu1-xLax) 2Ti2O7 and (Sm1-xLax) 2Ti2O7 solid solutions were well studied. (AxLa1-x)Ti2O7 solid solutions were isomorphous with La2Ti2O7 when x was less than 0.5 for (EuxLa1-x)Ti2O7 and 0.8 for (SmxLa1-x)Ti2O7. When x was above their solubility limit, a biphase was observed. The XRD and Raman data suggested that the biphase consisted of (AxLa1-x)2Ti2O7 perovskite-like layered structure and pure Sm2Ti2O7 pyrochlore structure. Ferroelectric domain switching was observed in the I-E and P-E hysteresis loops for textured (SmxLa1-x)Ti2O7 (x < 0.2). The highest d33 was 2.8 pC/N for (Sm0.1La0.9)Ti2O7. In the second part, The Pr3Ti2TaO11 compound was demonstrated to have a 3-layer type II AnBnO3n+2 PLS structure belonging to space group Pmc21 with unit cell parameters a = 3.8689(3) Å, b = 20.389(2) Å, c = 5.5046(5) Å, and its ferroelectric properties were investigated. Analysis of the XRD and TEM results showed that Pr3Ti2TaO11 ceramics have an n = 3 (type II) heteroblock structure consisting of alternating n = 2 and n = 4 octahedral oxide layers. High resolution electron microscopy revealed the layered structure to be highly disordered, with faulting of the heteroblock structure and the coexistence of a n = 4 phase on a fine scale (nm), which was evident as a broadening of the XRD peaks of the ceramics. Pr3Ti2TaO11 ceramic exhibits a super-high Curie point (1415±5 °C). A small, but measurable piezoelectric constant d33 between 0.1 and 0.2 pC/N was detected for the samples poled above 900 °C under an electric field of 100~200 V/cm. Pure LaTaO4 powders with orthorhombic phase were be prepared by co-precipitation method. The orthorhombic LaTaO4 powders have a 2-layer perovskite-like layered structure with space group A21am, which was refined using Rietveld method. The single phase O-LaTaO4 ceramic was prepared using SPS with a slow cooling rate (20 °C/min). A d33 of 0.3 pC/N was obtained from the electric field induced orthorhombic phase. In the second part of this work, the ferroelectricity and piezoelectricity of CsBiNb2O7 with Dion-Jacobson type PLS structure was successfully demonstrated for the first time. The ferroelectricity and piezoelectricity of RbBiNb2O7, which have similar structure with CsBiNb2O7, were also fully studied. Highly textured 2-layer Dion-Jacobson ceramics ABiNb2O7 (A = Rb and Cs) were prepared by one-step SPS. High resolution TEM showed well ordered (0 0 1) lattice planes. Striped ferroelectric domains were observed using PFM. The ferroelectricity and piezoelectricity of CsBiNb2O7 has been demonstrated for the first time. The Tc of RbBiNb2O7 and CsBiNb2O7 are 1098±5 and 1033±5 °C, respectively. The piezoelectric constant of RbBiNb2O7 and CsBiNb2O7 were approximately 5 and 8 pC/N. Thermal depoling studies confirmed the Curie point and the stability of the piezoelectricity. Sr6Nb4TiO18 ceramics with non-centrosymmetric structure were successfully prepared, but no obvious evidence was found to prove its ferroelectricity. The untextured and textured 6-layer Hexagonal compound Sr6Nb4TiO18 was prepared by solid state reaction and spark plasma sintering. Its Curie point was found to be greater than 1500 °C. No ferroelectric properties were observed by studying of I-E and P-E loops, and no d33 was observed after poling.
Supervisor: Not available Sponsor: Not available
Qualification Name: Thesis (Ph.D.) Qualification Level: Doctoral
EThOS ID:  DOI: Not available
Keywords: Engineering ; Materials Science ; Perovskite-like layered structured compounds ; ferroelectricity ; piezoelectricity