A General Synthetic Route to High-Quality Perovskite Oxide Nanoparticles and Their Enhanced Solar Photocatalytic Activity.

The main limitations of current methods for synthesizing perovskite oxide (ABO3 ) nanoparticles (NPs), e.g., the high reagent costs and sophisticated equipment, the long time and high-temperature processing, or multiple post-processing and thermal treatment steps, hamper their full study and potential application. Here, we use a facile low temperature (50 °C) chemical bath synthesis and only one annealing step to successfully produce high phase purity and crystalline quality nano-shaped rare-earth-based REMO3 NPs (RE=La, Nd, Sm, Gd; M=Fe, Mn, Al). We also show the versatility of this approach by fabricating La0.7 Sr0.3 MnO3 solid solution and non-RE-based BiFeO3 perovskite. To assess the potential of the as-prepared REFeO3 and REMnO3 NPs, they are used for photocatalytic degradation of the norfloxacin antibiotic and show high efficiency. We believe this easy, robust, versatile, and general route for synthesizing ABO3 -based NPs can be further explored in the vast perovskite family and beyond.

Crystal Growth Mechanisms of BiFeO3 Nanoparticles.

A wet-chemical synthesis process was designed to obtain reproducible single-phase multiferroic BiFeO3 nanoparticles. The phase purity, single crystallinity, and size of the nanoparticles are confirmed through the analysis of X-ray diffraction patterns, Raman spectroscopy, and high resolution transmission electron microscopy experiments. Crystal nucleation happens within the amorphous-rich area in multiple seeds, leading to the formation of single crystalline nanoparticles with no preferential faceting. Crystallization mechanisms of BiFeO3 nanoparticles were investigated following the Kissinger-Akahira-Sunose approach, indicating that two crystallization steps are responsible of the complete BiFeO3 nanoparticle formation. The first crystallization step involves a maximum of 70% of the final crystal volume, arising from nanocrystal nucleation and growth. The second step occurs above this threshold crystal volume fraction, and it is related to the nanocrystallite coalescence process. Analysis of the thermodynamic process of the crystallization of BiFeO3 nanoparticles following Ostwald rules suggests a relatively low energy barrier for crystal nucleation, highlighting that phase pure, single crystalline BiFeO3 nanoparticles are obtained using the present optimized wet-chemical synthesis process, with temperatures as low as 450 °C.

Negative-pressure-induced enhancement in a freestanding ferroelectric.

Ferroelectrics are widespread in technology, being used in electronics and communications, medical diagnostics and industrial automation. However, extension of their operational temperature range and useful properties is desired. Recent developments have exploited ultrathin epitaxial films on lattice-mismatched substrates, imposing tensile or compressive biaxial strain, to enhance ferroelectric properties. Much larger hydrostatic compression can be achieved by diamond anvil cells, but hydrostatic tensile stress is regarded as unachievable. Theory and ab initio treatments predict enhanced properties for perovskite ferroelectrics under hydrostatic tensile stress. Here we report negative-pressure-driven enhancement of the tetragonality, Curie temperature and spontaneous polarization in freestanding PbTiO3 nanowires, driven by stress that develops during transformation of the material from a lower-density crystal structure to the perovskite phase. This study suggests a simple route to obtain negative pressure in other materials, potentially extending their exploitable properties beyond their present levels.

Giant ultrafast photo-induced shear strain in ferroelectric BiFeO3.

Generation of strain using light is a key issue for future development of ultrasonic devices. Up to now, photo-induced GHz-THz acoustic phonons have been mainly explored in metals and semiconductors, and in artificial nanostructures to enhance their phononic emission. However, despite their inherent strong polarization (providing natural asymmetry) and superior piezoelectric properties, ferroelectric oxides have been only poorly regarded. Here, by using ultrafast optical pump-probe measurements, we show that photogeneration/photodetection of coherent phonons in BiFeO3 ferroelectric leads, at room temperature, to the largest intensity ratio ever reported of GHz transverse acoustic wave versus the longitudinal one. It is found that the major mechanism involved corresponds to screening of the internal electric fields by light-induced charges, which in turn induces stress by inverse piezoelectric effect. This giant opto-acoustic response opens new perspectives for the use of ferroelectric oxides in ultrahigh frequency acoustic devices and the development of new GHz-THz acoustic sources.

Phase transition at a nanometer scale detected by acoustic emission within the cubic phase Pb(Zn1/3Nb2/3)O3-xPbTiO3 relaxor ferroelectrics.

Pb(Zn(1/3)Nb(2/3))O3-xPbTiO(3) (x=4.5%-12%) relaxor ferroelectric crystals have been studied by means of acoustic emission (AE) in the 400-540 K temperature range. An anomalous AE activity independent of the ground state relaxor/morphotropic/ferroelectric crossover has been revealed at around 500 K, and it is associated with the "waterfall" feature related to the existence of polar nanoregions (PNRs). The 500 K AE anomaly is attributed to local martensitelike cubic-to-tetragonal ferroelectric transitions within the PNRs imbedded in a nonpolar (cubic) matrix.