Piezoelectric materials find important applications in micro- and nano-electromechanical systems (MEMS/NEMS). Pb(Zrx,Ti1-x)O3 (PZT) is currently the most widely used composition for such applications but due to environmental concerns over the toxicity of lead, lead free alternative materials are required. K0.5Na0.5NbO3 (KNN) is considered as a potential lead free piezoelectric but the current generation of monolithic ceramics has inferior electromechanical properties as compared to PZT. Consequently, there is great interest in improving the piezoelectric properties of KNN ceramics and various methods such as doping, hot-pressing and texturing are currently being studied. KNN single crystals like lead based single crystals have shown better electromechanical properties as compared to their ceramic counterparts. In addition, the behavior of a ferroelectric is largely dependent on its local domain response to an applied electrical or mechanical loading. Therefore, to understand better the material’s macroscopic properties, it is essential to access local ferroelectric domains behavior which collectively determines the electromechanical performance.

X-ray powder diffraction data are presented for nine new phases with the tetragonal tungsten bronze structure. By comparison with the structure of the M=Nb,RE=La analogue, these contain Ba in the large pentagonal sites with coordination number 15, a range of large rare-earth cations and Bi in the twelve coordinate sites, and the smaller cations, Ti and either Nb or Ta, in the octahedral framework sites. The a lattice parameter data of the tetragonal unit cell show an approximately linear variation with trivalent ion radius, apart from Dy, whose value appears to be anomalous; data for c show little variation with trivalent ion radius.

High dielectric constant important for functional electronic applications have been reported in the Sr1-1.5xYxTiO3 ceramic system with a maximum value for x = 0.01 coincident with the maximum grain size. This observation points to a possible correlation between the dielectric response and the microstructure of these ceramics. A solid solubility limit around x = 0.04 was reported recently by Fu et al., although the second phase was observed by X-ray diffraction only for x = 0.07. Therefore, the structure, microstructure and local composition of Sr1-1.5xYxTiO3 ceramics (x = 0 − 0.05) prepared by conventional mixed oxide method is investigated in this work by transmission electron microscopy (TEM) and scanning electron microscopy (SEM) equipped with energy dispersive spectroscopy facilities.

High-throughput synthesis of the ferroelectric solid solution Pb(Zr1−xTix)O3 (PZT) on single Pt/Ti/SiO2/Si substrates was demonstrated using a modified molecular beam epitaxy (MBE) system. The PZT films exhibited a phase transition from rhombohehdral (R) to tetragonal (T) symmetry as a function of Zr:Ti ratio, across the substrate diagonal. This was consistent with the presence of a morphotropic phase boundary (MPB) at a Zr:Ti ratio of 0.64:0.36, different from the value of 0.53:0.47 observed for bulk ceramics. All points on the films exhibited ferroelectric hysteresis loops. The results demonstrate the feasibility of high-throughput MBE for deposition of complex ferroelectric oxides, and pave the way for further materials discovery, in particular Pb-free piezoceramics.

Transmission electron microscopy, x-ray diffraction, relative permittivity as a function of temperature, and polarization versus field loops were used to study the antiferroelectric/ferroelectric (AFE/FE) phase boundary in Pb1–1.5xLaxZr0.9Ti0.1O3 (PLZT, 100x/90/10) ceramics. X-ray diffraction and electrical measurements indicated a FE rhombohedral (R) to AFE tetragonal (T) phase transition between PLZT 2/90/10 and 4/90/10. Both phases exhibited superstructure reflections in electron-diffraction patterns at ½{hkl} positions consistent with rotations of the octahedra in antiphase. Previously, neutron diffraction suggested that the FER has an a−a−a− tilt system (Glazer notation), in agreement with its macroscopic symmetry. By analogy, it is proposed that the AFET phase has an a0a0c− tilt system. The AFE phase was also characterized by incommensurate superstructure along pseudocubic 〈110〉p directions, whereas the FE phase had extra commensurate superlattice reflections at 1/2{hk0}p positions. 1/2{hk0}p reflections are forbidden in both tilt systems, but their presence is explained by Pb ion displacements averaged along 〈111〉 but with short coherence antiparallel components along 〈110〉 directions. The antiparallel Pb displacements are coupled to an a−b−b− (a ≈ b) monoclinic tilt system in the vicinity of the AFE/FE boundary.

Advanced analytical transmission electron microscopy has been used to investigate microstructural evolution during pyrolysis in triol-based sol-gel thin films. At pyrolysis temperatures up to 300 °C, the films remained amorphous; however, nanometer-sized precipitates were observed in films heat-treated up to 400 °C for 10 min. Analytical transmission electron microscopy indicated that the precipitates were Pb-rich, as well as deficient in O, Ti, and Zr. Films pyrolyzed up to 500 °C for 10 min were composed of a nanocrystalline pyrochlore phase; however, pores could be observed, situated in the same position as the nanometer-sized precipitates at 400 °C. Face-centered cubic Pb-rich crystallites were also present on the surface of pyrolyzed films but absent in the fully crystallized films annealed at 650 °C. A tentative mechanism is proposed to explain these observations.

The crystal structure of Bi2Zn2/3Nb4/3O7 was determined using a combination of electron, x-ray, and neutron powder diffraction. The compound crystallizes with a monoclinic zirconolite-like structure [C2/c (No.15) space group, a = 13.1037(9) Å, b = 7.6735(3) Å, c = 12.1584(6) Å, β = 101.318(5)°]. According to structural refinement using neutron diffraction data, Nb preferentially occupies six-fold coordinated sites in octahedral sheets parallel to the (001) planes, while Zn is statistically distributed between two half-occupied (5 + 1)-fold coordinated sites near the centers of six-membered rings of [Nb(Zn)O6] octahedra. The Nb/Zn cation layers alternate along the c-axis with Bi-layers, in which Bi cations occupy both eight- and seven-fold coordinated sites. The eight-fold coordinated Bi atoms exhibited strongly anisotropic thermal displacements with an abnormally large component directed approximately along the c-axis (normal to the octahedral layers).

The structures and microstructures of a range of Aurivillius phases were investigated by transmission electron microscopy. Systematic rows of superlattice reflections arising from tilting of octahedra around the c axis were identified, and their intensities at room temperature were shown to diminish as the tolerance factor (t) of the perovskite blocks increased. For compounds with t's approaching 1, no superlattice reflections were observed. the paraelectric-to-ferroelectric phase transition temperature (Tc) was monitored through permittivity measurements as a function of temperature, and Tc was also shown to decrease as t increased. Consequently, the onset of octahedral tilting and Tc appeared to be strongly related Aurivillius phases. Planar defects arising from the structural phase transitions and from stacking irregularities were also discussed.

The structures and microstructures of a range of Aurivillius phases have been investigated using transmission electron microscopy. Superlattice reflections arising from rotations of octahedra around the c-axis have been identified and their intensity at room temperature has been shown to diminish as the tolerance factor of the perovskite blocks increases. The paraelectric to ferroelectric phase transition temperature (Tc) has been monitored using permittivity measurements as a function of temperature and Tc has also been shown to decrease as tolerance factor increases. It is proposed that the onset of octahedral tilting and Tc are related in Aurivillius phases.

The domain structure and dielectric properties as a function of lanthanum concentration and Zr/Ti ratio have been investigated in rhombohedral and tetragonal lead lanthanum zirconate titanate (PLZT) ceramics. Transmission electron microscopy revealed that, with increasing lanthanum concentration and Zr/Ti ratio, the long-range-ordered domains (macrodomains) reduced in width, initially being fine scale (20 nm) striations, but eventually forming a “mottled” contrast (5 nm), characteristic of a relaxor. Relative permittivity measurements as a function of temperature revealed a correlation between broadening of the dielectric maxima and the onset of relaxor-type behavior with the appearance of the striations and mottled (relaxor) contrast, respectively.

The nucleation, growth, and orientation of lead zirconate titanate thin films prepared from organometallic precursor solutions by spin coating on (111) oriented platinum substrates and crystallized by rapid thermal annealing was investigated. The effects of pyrolysis temperature, post-pyrolysis thermal treatments, and excess lead addition are reported. The use of post-pyrolysis oxygen anneals at temperatures in the regime of 350–450 °C was found to strongly affect the kinetics of subsequent amorphous-pyrochlore-perovskite crystallization by rapid thermal annealing. The use of such post-pyrolysis anneals allowed films of reproducible microstructure and textures [both (100) and (111)] to be prepared by rapid thermal annealing. It is proposed that such anneals and pyrolysis temperature affect the oxygen concentration/average Pb valence in the amorphous films prior to annealing. Such changes in the Pb valence state then affect the stability of the transient pyrochlore phase and thus the kinetics of perovskite crystallization.