Mesoporous TiO2 anatase films for enhanced photocatalytic activity under UV and visible light.

Mesoporous TiO2 films with enhanced photocatalytic activity in both UV and visible wavelength ranges were developed through a non-conventional atomic layer deposition (ALD) process at room temperature. Deposition at such a low temperature promotes the accumulation of by-products in the amorphous TiO2 films, caused by the incomplete hydrolysis of the TiCl4 precursor. The additional thermal annealing induces the fast recrystallisation of amorphous films, as well as an in situ acidic treatment of TiO2. The interplay between the deposition parameters, such as purge time, the amount of structural defects introduced and the enhancement of the photocatalytic properties from different mesoporous films clearly shows that our easily upscalable non-conventional ALD process is of great industrial interest for environmental remediation and other photocatalytic applications, such as hydrogen production.

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.

Ultrafast acousto-optic mode conversion in optically birefringent ferroelectrics.

The ability to generate efficient giga-terahertz coherent acoustic phonons with femtosecond laser makes acousto-optics a promising candidate for ultrafast light processing, which faces electronic device limits intrinsic to complementary metal oxide semiconductor technology. Modern acousto-optic devices, including optical mode conversion process between ordinary and extraordinary light waves (and vice versa), remain limited to the megahertz range. Here, using coherent acoustic waves generated at tens of gigahertz frequency by a femtosecond laser pulse, we reveal the mode conversion process and show its efficiency in ferroelectric materials such as BiFeO3 and LiNbO3. Further to the experimental evidence, we provide a complete theoretical support to this all-optical ultrafast mechanism mediated by acousto-optic interaction. By allowing the manipulation of light polarization with gigahertz coherent acoustic phonons, our results provide a novel route for the development of next-generation photonic-based devices and highlight new capabilities in using ferroelectrics in modern photonics.

Giant Optical Polarization Rotation Induced by Spin-Orbit Coupling in Polarons.

We have uncovered a giant gyrotropic magneto-optical response for doped ferromagnetic manganite La_{2/3}Ca_{1/3}MnO_{3} around the near room-temperature paramagnetic-to-ferromagnetic transition. At odds with current wisdom, where this response is usually assumed to be fundamentally fixed by the electronic band structure, we point to the presence of small polarons as the driving force for this unexpected phenomenon. We explain the observed properties by the intricate interplay of mobility, Jahn-Teller effect, and spin-orbit coupling of small polarons. As magnetic polarons are ubiquitously inherent to many strongly correlated systems, our results provide an original, general pathway towards the generation of magnetic-responsive gigantic gyrotropic responses that may open novel avenues for magnetoelectric coupling beyond the conventional modulation of magnetization.

Photovoltaics with Ferroelectrics: Current Status and Beyond.

Ferroelectrics carry a switchable spontaneous electric polarization. This polarization is usually coupled to strain, making ferroelectrics good piezoelectrics. When coupled to magnetism, they become so-called multiferroic systems, a field that has been widely investigated since 2003. While ferroelectrics are birefringent and non-linear optically transparent materials, the coupling of polarization with optical properties has received, since 2009, renewed attention, triggered notably by low-bandgap ferroelectrics suitable for sunlight spectrum absorption and original photovoltaic effects. Consequently, power conversion efficiencies up to 8.1% were recently achieved and values of 19.5% were predicted, making photoferroelectrics promising photovoltaic alternatives. This article aims at providing an up-to-date review on this emerging and rapidly progressing field by highlighting several important issues and parameters, such as the role of domain walls, ways to tune the bandgap, consequences arising from the polarization switchability, and the role of defects and contact electrodes, as well as the downscaling effects. Beyond photovoltaicity, other polarization-related processes are also described, like light-induced deformation (photostriction) or light-assisted chemical reaction (photostriction). It is hoped that this overview will encourage further avenues to be explored and challenged and, as a byproduct, will inspire other research communities in material science, e.g., so-called hybrid halide perovskites.

Polarization Rotation in Ferroelectric Tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 Superlattices.

In ferroelectric thin films, controlling the orientation of the polarization is a key element to controlling their physical properties. We use laboratory and synchrotron X-ray diffraction to investigate ferroelectric bicolor PbTiO3/PbZr0.2Ti0.8O3 and tricolor PbTiO3/SrTiO3/PbZr0.2Ti0.8O3 superlattices and to study the role of the SrTiO3 layers on the domain structure. In the tricolor superlattices, we demonstrate the existence of 180° ferroelectric stripe nanodomains, induced by the depolarization field produced by the SrTiO3 layers. Each ultrathin SrTiO3 layer modifies the electrostatic boundary conditions between the ferroelectric layers compared to the corresponding bicolor structures, leading to the suppression of the a/c polydomain states. Combined with the electrostatic effect, the tensile strain induced by PbZr0.2Ti0.8O3 in the PbTiO3 layers leads to polarization rotation in the system as evidenced by grazing incidence X-ray measurements. This polarization rotation is associated with the monoclinic Mc phase as revealed by the splitting of the (HHL) and (H0L) reciprocal lattice points. This work demonstrates that the tricolor paraelectric/ferroelectric superlattices constitute a tunable system to investigate the concomitant effects of strains and depolarizing fields. Our studies provide a pathway to stabilize a monoclinic symmetry in ferroelectric layers, which is of particular interest for the enhancement of the piezoelectric properties.

A New Method Combining Finite Element Analysis and Digital Image Correlation to Assess Macroscopic Mechanical Properties of Dentin.

A literature review points out a large discrepancy in the results of the mechanical tests on dentin that can be explained by stress and strain assessment during the tests. Errors in these assessments during mechanical tests can lead to inaccurate estimation of the mechanical properties of the tested material. On top of that, using the beam theory to analyze the bending test for thick specimens will increase these experimental errors. After summarizing the results of mechanical tests on dentin in the literature, we focus on bending tests and compare the stress assessment obtained by finite element analysis (FEA) and by beam theory application. We show that the difference between the two methods can be quite large in some cases, leading us to prefer the use of FEA to assess stresses. We then propose a new method based on coupling finite element analysis and digital image correlation (DIC) to more accurately evaluate stress distributions, strain distributions and elastic modulus in the case of a three-point bending test. To illustrate and prove the feasibility of the method, it is applied on a dentinal sample so that mean elastic modulus and maximum tensile stress are obtained (11.9 GPa and 143.9 MPa). Note that the main purpose of this study is to focus on the method itself, and not to provide new mechanical values for dentin. When used in standard mechanical testing of dentin, this kind of method should help to narrow the range of obtained mechanical properties values.

Giant room-temperature elastocaloric effect in ferroelectric ultrathin films.

Environmentally friendly ultrathin BaTiO3 capacitors can exhibit a giant stress-induced elastocaloric effect without hysteresis loss or Joule heating. By combining this novel elastocaloric effect with the intrinsic electrocaloric effect, an ideal refrigeration cycle with high performance (temperature change over 10 K with a wide working-temperature window of 60 K) at room temperature is proposed for future cooling applications.

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.