Shaping single crystalline BaTiO3 nanostructures by focused neon or helium ion milling.

The realization of perovskite oxide nanostructures with controlled shape and dimensions remains a challenge. Here, we investigate the use of helium and neon focused ion beam (FIB) milling in an ion microscope to fabricate BaTiO3 nanopillars of sub-500 nm diameter from BaTiO3 (001) single crystals. Irradiation of BaTiO3 with He ions induces the formation of nanobubbles inside the material eventually leading to surface swelling and blistering. Ne FIB is shown to be suitable for milling without inducing surface swelling. The resulting defect-free single crystal nanostructures are enveloped by a neon-rich amorphous and a point defect-rich crystalline layers both on top and lateral sides. The amorphous shell can be selectively removed by dipping the nanostructures in diluted HF. The geometry and beam-induced damage of the milled nanostructures depend strongly on the patterning parameters and can be well controlled. Ne ion milling is shown to be an effective method to rapidly prototype BaTiO3 crystalline nanostructures.

Electrically induced cancellation and inversion of piezoelectricity in ferroelectric Hf0.5Zr0.5O2.

HfO2-based thin films hold huge promise for integrated devices as they show full compatibility with semiconductor technologies and robust ferroelectric properties at nanometer scale. While their polarization switching behavior has been widely investigated, their electromechanical response received much less attention so far. Here, we demonstrate that piezoelectricity in Hf0.5Zr0.5O2 ferroelectric capacitors is not an invariable property but, in fact, can be intrinsically changed by electrical field cycling. Hf0.5Zr0.5O2 capacitors subjected to ac cycling undergo a continuous transition from a positive effective piezoelectric coefficient d33 in the pristine state to a fully inverted negative d33 state, while, in parallel, the polarization monotonically increases. Not only can the sign of d33 be uniformly inverted in the whole capacitor volume, but also, with proper ac training, the net effective piezoresponse can be nullified while the polarization is kept fully switchable. Moreover, the local piezoresponse force microscopy signal also gradually goes through the zero value upon ac cycling. Density functional theory calculations suggest that the observed behavior is a result of a structural transformation from a weakly-developed polar orthorhombic phase towards a well-developed polar orthorhombic phase. The calculations also suggest the possible occurrence of a non-piezoelectric ferroelectric Hf0.5Zr0.5O2. Our experimental findings create an unprecedented potential for tuning the electromechanical functionality of ferroelectric HfO2-based devices.

Flexo-photovoltaic effect.

It is highly desirable to discover photovoltaic mechanisms that enable enhanced efficiency of solar cells. Here we report that the bulk photovoltaic effect, which is free from the thermodynamic Shockley-Queisser limit but usually manifested only in noncentrosymmetric (piezoelectric or ferroelectric) materials, can be realized in any semiconductor, including silicon, by mediation of flexoelectric effect. We used either an atomic force microscope or a micrometer-scale indentation system to introduce strain gradients, thus creating very large photovoltaic currents from centrosymmetric single crystals of strontium titanate, titanium dioxide, and silicon. This strain gradient-induced bulk photovoltaic effect, which we call the flexo-photovoltaic effect, functions in the absence of a p-n junction. This finding may extend present solar cell technologies by boosting the solar energy conversion efficiency from a wide pool of established semiconductors.

Unidirectional Spin-Dependent Molecule-Ferromagnet Hybridized States Anisotropy in Cobalt Phthalocyanine Based Magnetic Tunnel Junctions.

Organic or molecular spintronics is a rising field of research at the frontier between condensed matter physics and chemistry. It aims to mix spin physics and the richness of chemistry towards designing new properties for spin electronics devices through engineering at the molecular scale. Beyond the expectation of a long spin lifetime, molecules can be also used to tailor the spin polarization of the injected current through the spin-dependent hybridization between molecules and ferromagnetic electrodes. In this Letter, we provide direct evidence of a hybrid interface spin polarization reversal due to the differing hybridization between phthalocyanine molecules and each cobalt electrode in Co/CoPc/Co magnetic tunnel junctions. Tunnel magnetoresistance and anisotropic tunnel magnetoresistance experiments show that interfacial hybridized electronic states have a unidirectional anisotropy that can be controlled by an electric field and that spin hybridization at the bottom and top interfaces differ, leading to an inverse tunnel magnetoresistance.

Room-temperature ferroelectricity in hexagonal TbMnO3 thin films.

Piezoresponse force microscopy imaging in conjunction with first-principles calculations provide strong evidence for room-temperature ferroelectricity in epitaxially stabilized hexagonal TbMnO3 thin films, which in the bulk form are with orthorhombic structure. The obtained results demonstrate that new phases and functional properties of complex oxide materials can be strain-engineered using epitaxial growth.

Ferroelectricity in highly ordered arrays of ultra-thin-walled Pb(Zr,Ti)O3 nanotubes composed of nanometer-sized perovskite crystallites.

We report the first unambiguous ferroelectric properties of ultra-thin-walled Pb(Zr,Ti)O 3 (PZT) nanotube arrays, each with 5 nm thick walls and outer diameters of 50 nm. Ferroelectric switching behavior with well-saturated hysteresis loops is observed in these ferroelectric PZT nanotubes with P r and E c values of about 1.5 microC cm (-2) and 86 kV cm (-1), respectively, for a maximum applied electric field of 400 kV cm (-1). These PZT nanotube arrays (10 (12) nanotubes cm (-2)) might provide a competitive approach toward the development of three-dimensional capacitors for the terabyte ferroelectric random access memory.