Over the last few years the efforts devoted to the research on low-temperature processing of metal oxide thin films have increased notably. This has enabled the direct integration of metal oxide layers (amorphous semiconductors) on low-melting-point polymeric substrates for flexible electronic systems, which adds to the economic and environmental benefits of the use of these processes with reduced energy consumption. More challenging is the preparation of crystalline complex oxide films at temperatures compatible with their direct integration in flexible devices. However, the usually high crystallization temperatures (>600 °C) impede the development of devices that take full advantage of the large variety of oxide functionalities available. This tutorial review analyzes a number of strategies based on wet chemical methods for inducing the crystallization of metal oxide thin films at low temperatures. The key mechanisms are explained in relation to the specific step of the fabrication process reached in an earlier stage: the formation of a defect-free, highly densified amorphous metal-oxygen network or the actual crystallization of the metal oxide. The role of photochemistry, where light can be used as a complementary energy source to induce crystallization, is particularly highlighted. This requires the synthesis of novel photosensitive solutions (modified metal alkoxides, charge-transfer metal complexes or structurally designed molecular compounds) and a precise control over the reactions promoted by UV irradiation (photochemical cleavage, ozonolysis, condensation or photocatalysis). Relevant examples derived from the integration of crystalline metal oxide thin films on flexible substrates (≤350 °C) illustrate the most recent achievements in this field.
The peculiar features of domain walls observed in ferroelectrics make them promising active elements for next-generation non-volatile memories, logic gates and energy-harvesting devices. Although extensive research activity has been devoted recently to making full use of this technological potential, concrete realizations of working nanodevices exploiting these functional properties are yet to be demonstrated. Here, we fabricate a multiferroic tunnel junction based on ferromagnetic LaSrMnO electrodes separated by an ultrathin ferroelectric BaTiO tunnel barrier, where a head-to-head domain wall is constrained. An electron gas stabilized by oxygen vacancies is confined within the domain wall, displaying discrete quantum-well energy levels. These states assist resonant electron tunnelling processes across the barrier, leading to strong quantum oscillations of the electrical conductance.
Transmission electron microscopy and neutron diffraction have been used to characterize ceramics and single crystals from the rhombohedral region of the (x = 0.06-0.45) phase diagram. Electron diffraction patterns showed the existence of superlattice reflections of the type , where h = k = l, and , which are not observed by neutron powder diffraction. The analysis of these reflections also revealed satellite spots around the , which are associated with periodic antiphase boundaries. The origin of these superlattice reflections is explained by the existence of local regions presenting antiparallel cation displacements, and models for this are suggested
The character of the ferroelectric domains in lead zirconate titanate (PbZr1-x
Tix
O3
- PZT) ceramics has been studied using transmission electron microscopy (TEM) for compositions right across the rhombohedral phase (x
= 0.06 to x
= 0.45). The polarization hysteresis has also been determined for the same specimens and it has been demonstrated that the compositions between x
= 0.12 and x
= 0.40 show double hysteresis loops. It is shown that the occurrence of domain walls which do not correspond exactly to crystallographic planes produces generalized wedge-shaped domains, instead of the typical bands of parallel-sided domains reported in most ferroelectrics. A systematic variation in the arrangement of the domain walls as the composition progresses across the rhombohedral region is reported for the first time. This result is related to the occurrence of double hysteresis loops for these compositions. The role of oxygen octahedral tilts of the low temperature rhombohedral phase in the formation of the domains and in the hysteresis behaviour is discussed.
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