Giant electromechanical coupling of relaxor ferroelectrics controlled by polar nanoregion vibrations.

Relaxor-based ferroelectrics are prized for their giant electromechanical coupling and have revolutionized sensor and ultrasound applications. A long-standing challenge for piezoelectric materials has been to understand how these ultrahigh electromechanical responses occur when the polar atomic displacements underlying the response are partially broken into polar nanoregions (PNRs) in relaxor-based ferroelectrics. Given the complex inhomogeneous nanostructure of these materials, it has generally been assumed that this enhanced response must involve complicated interactions. By using neutron scattering measurements of lattice dynamics and local structure, we show that the vibrational modes of the PNRs enable giant coupling by softening the underlying macrodomain polarization rotations in relaxor-based ferroelectric PMN-xPT {(1 - x)[Pb(Mg1/3Nb2/3)O3] - xPbTiO3} (x = 30%). The mechanism involves the collective motion of the PNRs with transverse acoustic phonons and results in two hybrid modes, one softer and one stiffer than the bare acoustic phonon. The softer mode is the origin of macroscopic shear softening. Furthermore, a PNR mode and a component of the local structure align in an electric field; this further enhances shear softening, revealing a way to tune the ultrahigh piezoelectric response by engineering elastic shear softening.

Orbital engineering in symmetry-breaking polar heterostructures.

We experimentally demonstrate a novel approach to substantially modify orbital occupations and symmetries in electronically correlated oxides. In contrast to methods using strain or confinement, this orbital tuning is achieved by exploiting charge transfer and inversion symmetry breaking using atomically layered heterostructures. We illustrate the technique in the LaTiO_{3}-LaNiO_{3}-LaAlO_{3} system; a combination of x-ray absorption spectroscopy and ab initio theory reveals electron transfer and concomitant polar fields, resulting in a ∼50% change in the occupation of Ni d orbitals. This change is sufficiently large to remove the orbital degeneracy of bulk LaNiO_{3} and creates an electronic configuration approaching a single-band Fermi surface. Furthermore, we theoretically show that such three-component heterostructuring is robust and tunable by choice of insulator in the heterostructure, providing a general method for engineering orbital configurations and designing novel electronic systems.

Metallization of vanadium dioxide driven by large phonon entropy.

Phase competition underlies many remarkable and technologically important phenomena in transition metal oxides. Vanadium dioxide (VO2) exhibits a first-order metal-insulator transition (MIT) near room temperature, where conductivity is suppressed and the lattice changes from tetragonal to monoclinic on cooling. Ongoing attempts to explain this coupled structural and electronic transition begin with two alternative starting points: a Peierls MIT driven by instabilities in electron-lattice dynamics and a Mott MIT where strong electron-electron correlations drive charge localization. A key missing piece of the VO2 puzzle is the role of lattice vibrations. Moreover, a comprehensive thermodynamic treatment must integrate both entropic and energetic aspects of the transition. Here we report that the entropy driving the MIT in VO2 is dominated by strongly anharmonic phonons rather than electronic contributions, and provide a direct determination of phonon dispersions. Our ab initio calculations identify softer bonding in the tetragonal phase, relative to the monoclinic phase, as the origin of the large vibrational entropy stabilizing the metallic rutile phase. They further reveal how a balance between higher entropy in the metal and orbital-driven lower energy in the insulator fully describes the thermodynamic forces controlling the MIT. Our study illustrates the critical role of anharmonic lattice dynamics in metal oxide phase competition, and provides guidance for the predictive design of new materials.

Strain-driven oxygen deficiency in self-assembled, nanostructured, composite oxide films.

Oxide self-assembly is a promising bottom-up approach for fabricating new composite materials at the nanometer length scale. Tailoring the properties of such systems for a wide range of electronic applications depends on the fundamental understanding of the interfaces between the constituent phases. We show that the nanoscale strain modulation in self-assembled systems made of high-T(c) superconducting films containing nanocolumns of BaZrO(3) strongly affects the oxygen composition of the superconductor. Our findings explain the observed reduction of the superconducting critical temperature.