Search

Solid-state materials are currently being explored as a platform for the manipulation of spins for spintronics and quantum information science. More broadly, a wide spectrum of ferroelectric materials, spanning from inorganic oxides to polymeric systems such as PVDF, present a different approach to explore quantum phenomena in which the spins are set and manipulated with electric fields. Using dilute Fe

Author(s): Hong, Zijian; Das, Sujit; Nelson, Christopher; Yadav, Ajay; Wu, Yongjun; Junquera, Javier; Chen, Long-Qing; Martin, Lane W; Ramesh, Ramamoorthy | Abstract: Controlling the domain formation in ferroelectric materials at the nanoscale is a fertile ground to explore emergent phenomena and their technological prospects. For example, charged ferroelectric domain walls in BiFeO3 and ErMnO3 exhibit significantly enhanced conductivity which could serve as the foundation for next-generation circuits (Estevez and Laurson, Phys. Rev. B 2015, 91, 054407). Here, we describe a concept in which polar vortices perform the same role as a ferroelectric domain wall in classical domain structures with the key difference being that the polar vortices can accommodate charged (i.e., head-to-head and tail-to-tail) domains, for example, in ferroelectric PbTiO3/dielectric SrTiO3 superlattices. Such a vortex domain wall structure can be manipulated in a reversible fashion under an external applied field.

The ultimate challenge for the development of new multiferroics with enhanced properties lies in achieving nanoscale control of the coupling between different ordering parameters. In oxide-based multiferroics, substitutional cation dopants offer the unparalleled possibility to modify both the electric and magnetic properties at a local scale. Herein it is demonstrated the formation of a dopant-controlled polar pattern in BiFeO3 leading to the spontaneous instauration of periodic polarization waves. In particular, nonpolar Ca-doped rich regions act as spacers between consecutive dopant-depleted regions displaying coupled ferroelectric states. This alternation of layers with different ferroelectric state creates a novel vertical polar structure exhibiting giant polarization gradients as large as 70 μC cm–2 across 30 A thick domains. The drastic change in the polar state of the film is visualized using high-resolution differential phase-contrast imaging able to map changes in ferroelectric polarization at at...

A strain-driven orthorhombic (O) to rhombohedral (R) phase transition is reported in La-doped BiFeO3 thin films on silicon substrates. Biaxial compressive epitaxial strain is found to stabilize the rhombohedral phase at La concentrations beyond the morphotropic phase boundary (MPB). By tailoring the residual strain with film thickness, we demonstrate a mixed O/R phase structure consisting of O phase domains measuring tens of nanometers wide within a predominant R phase matrix. A combination of piezoresponse force microscopy (PFM), transmission electron microscopy (TEM), polarization–electric field hysteresis loop (P–E loop), and polarization maps reveal that the O-R structural change is an antiferroelectric to ferroelectric (AFE-FE) phase transition. Using scanning transmission electron microscopy (STEM), an atomically sharp O/R MPB is observed. Moreover, X-ray absorption spectra (XAS) and X-ray linear dichroism (XLD) measurements reveal a change in the antiferromagnetic axis orientation from out of plane...

Electric-field (E-field) control of magnetism enabled by multiferroic materials has the potential to revolutionize the landscape of present memory devices plagued with high energy dissipation. To date, this E-field controlled multiferroic scheme has only been demonstrated at room temperature using BiFeO3 films grown on DyScO3, a unique and expensive substrate, which gives rise to a particular ferroelectric domain pattern in BiFeO3. Here, we demonstrate reversible electric-field-induced switching of the magnetic state of the Co layer in Co/BiFeO3 (BFO) (001) thin film heterostructures fabricated on (001) SrTiO3 (STO) substrates. The angular dependence of the coercivity and the remanent magnetization of the Co layer indicates that its easy axis reversibly switches back and forth 45° between the (100) and the (110) crystallographic directions of STO as a result of alternating application of positive and negative voltage pulses between the patterned top Co electrode layer and the (001) SrRuO3 (SRO) layer on which the ferroelectric BFO is epitaxially grown. The coercivity (HC) of the Co layer exhibits a hysteretic behavior between two states as a function of voltage. A mechanism based on the intrinsic magnetoelectric coupling in multiferroic BFO involving projection of antiferromagnetic G-type domains is used to explain the observation. We have also measured the exact canting angle of the G-type domain in strained BFO films for the first time using neutron diffraction. These results suggest a pathway to integrating BFO-based devices on Si wafers for implementing low power consumption and nonvolatile magnetoelectronic devices.

The work is supported by U.S. Department of Energy, Office of Basic Energy Sciences, Division of Materials Sciences and Engineering under Award FG02-07ER46417 (L.-Q.C., F.X., and J.B.). Z.H. acknowledges the support by NSF-MRSEC Grant DMR-1420620 and NSF-MWN Grant DMR-1210588. A.R.D. acknowledges support from the Army Research Office under Grant W911NF-14-1-0104. L.W.M. acknowledges support from the National Science Foundation under Grant DMR-1451219. A.K.Y., C.T.N., and R.R. acknowledge support from the Office of Basic Energy Sciences, U.S. Department of Energy under contract no. DE-AC02-05CH11231. L.W.M. and R.R. acknowledge support from the Gordon and Betty Moore Foundation’s EPiQS Initiative, Grant GBMF5307. A novel mesoscale state comprising of an ordered polar vortex lattice has been demonstrated in ferroelectric superlattices of PbTiO3/SrTiO3. Here, we employ phase-field simulations, analytical theory, and experimental observations to evaluate thermodynamic conditions and geometric length scales that are critical for the formation of such exotic vortex states. We show that the stability of these vortex lattices involves an intimate competition between long-range electrostatic, long-range elastic, and short-range polarization gradient-related interactions leading to both an upper and a lower bound to the length scale at which these states can be observed. We found that the critical length is related to the intrinsic domain wall width, which could serve as a simple intuitive design rule for the discovery of novel ultrafine topological structures in ferroic systems. Postprint Postprint

The ultimate challenge for the development of new multiferroics with enhanced properties lies in achieving nanoscale control of the coupling between different ordering parameters. In oxide-based multiferroics, substitutional cation dopants offer the unparalleled possibility to modify both the electric and magnetic properties at a local scale. Herein it is demonstrated the formation of a dopant-controlled polar pattern in BiFeO

We report a voltage controlled reversible creation and annihilation of a-axis oriented ∼10 nm wide ferroelastic nanodomains without a concurrent ferroelectric 180° switching of the surrounding c-domain matrix in archetypal ferroelectric Pb(Zr0.2Ti0.8)O3 thin films by using the piezo-response force microscopy technique. In previous studies, the coupled nature of ferroelectric switching and ferroelastic rotation has made it difficult to differentiate the underlying physics of ferroelastic domain wall movement. Our observation of distinct thresholds for ferroelectric and ferroelastic switching allows us investigate the ferroelastic switching cleanly and demonstrate a new degree of nanoscale control over the ferroelastic domains.

Low temperature solution-processed organic-inorganic halide perovskite CH3NH3PbI3 has demonstrated great potential for photovoltaics and light emitting devices. Recent discoveries of long ambipolar carrier diffusion lengths and the prediction of the Rashba effect in CH3NH3PbI3, that possesses large spin-orbit coupling, also point to a novel semiconductor system with highly promising properties for spin-based applications. Through circular pump-probe measurements, we demonstrate that highly polarized electrons of total angular momentum (J) with an initial degree of polarization Pini ~ 90% (i.e., –30% degree of electron spin polarization) can be photogenerated in perovskites. Time-resolved Faraday rotation measurements reveal photo-induced Faraday rotation as large as 10°/μm at 200 K (at wavelength λ = 750 nm) from an ultrathin 70 nm film. These spin polarized carrier populations generated within the polycrystalline perovskite films, relax via intraband carrier spin-flip through the Elliot-Yafet mechanism. Through a simple two-level model, we elucidate the electron spin relaxation lifetime to be ~7 ps and that of the hole is ~1 ps. Our work highlights the potential of CH3NH3PbI3 as a new candidate for spintronics applications such as ultrafast spin switches, spin aligners or filters and possibly spin-polarized light emitters. Accepted version

A strain-driven orthorhombic (O) to rhombohedral (R) phase transition is reported in La-doped BiFeO

Electric-field (E-field) control of magnetism enabled by multiferroic materials has the potential to revolutionize the landscape of present memory devices plagued with high energy dissipation. To date, this E-field controlled multiferroic scheme has only been demonstrated at room temperature using BiFeO

Topological walls separating domains of continuous polarization, magnetization, and strain in ferroic materials hold promise of novel electronic properties, that are intrinsically localized on the nanoscale and that can be patterned on demand without change of material volume or elemental composition. We have revealed that ferroelectric domain walls in multiferroic BiFeO3 are inherently dynamic electronic conductors, closely mimicking memristive behavior and contrary to the usual assumption of rigid conductivity. Applied electric field can cause a localized transition between insulating and conducting domain walls, tune domain wall conductance by over an order of magnitude, and create a quasicontinuous spectrum of metastable conductance states. Our measurements identified that subtle and microscopically reversible distortion of the polarization structure at the domain wall is at the origin of the dynamic conductivity. The latter is therefore likely to be a universal property of topological defects in ferr...

We demonstrate a direct correlation between the domain structure of multiferroic BiFeO3 thin films and exchange bias of Co0.9Fe0.1/BiFeO3 heterostructures. Two distinct types of interactions, an enhancement of the coercive field (exchange enhancement) and an enhancement of the coercive field combined with large shifts of the hysteresis loop (exchange bias), have been observed in these heterostructures, which depend directly on the type and crystallography of the nanoscale (2 nm) domain walls in the BiFeO3 film. We show that the magnitude of the exchange bias interaction scales with the length of 109 degree ferroelectric domain walls in the BiFeO3 thin films which have been probed via piezoresponse force microscopy and x-ray magnetic circular dichroism., Comment: Accepted to Nano Letters May 2008

The performance of ferroelectric devices, for example, the ferroelectric field effect transistor, is reduced by the presence of crystal defects such as edge dislocations. For example, it is well-known that edge dislocations play a crucial role in the formation of ferroelectric dead-layers at interfaces and hence finite size effects in ferroelectric thin films. The detailed lattice structure including the relevant electro- mechanical coupling mechanisms in close vicinity of the edge dislocations is, however, not well-understood, which hampers device optimization. Here, we investigate edge dislocations in ferroelectric BiFeO3 by means of spherical aberration-corrected scanning transmission electron microscopy, a dedicated model-based structure analysis, and phase field simulations. Unit-cell-wise resolved strain and polarization profiles around edge dislocation reveal a wealth of material states including polymorph nanodomains and multiple domain walls characteristically pinned to the dislocation. We locally determine the piezoelectric tensor and identify piezoelectric coupling as the driving force for the observed phenomena, explaining, for example, the orientation of the domain wall with respect to the edge dislocation. Furthermore, an atomic model for the dislocation core is derived.

Various mechanisms are currently exploited to transduce a wide range of stimulating sources into mechanical motion. At the microscale, simultaneously high amplitude, high work output, and high speed in actuation are hindered by limitations of these actuation mechanisms. Here we demonstrate a set of microactuators fabricated by a simple microfabrication process, showing simultaneously high performance by these metrics, operated on the structural phase transition in vanadium dioxide responding to diverse stimuli of heat, electric current, and light. In both ambient and aqueous conditions, the actuators bend with exceedingly high displacement-to-length ratios up to 1 in the sub-100 μm length scale, work densities over 0.63 J/cm 3 , and at frequencies up to 6 kHz. The functionalities of actuation can be further enriched with integrated designs of planar as well as three-dimensional geometries. Combining the superior performance, high durability, diversity in responsive stimuli, versatile working environments, and microscale manufacturability, these actuators offer potential applications in microelectromechanical systems, microfluidics, robotics, drug delivery, and artificial muscles.

Metallic conductance in charged ferroelectric domain walls was predicted more than 40 years ago as the first example of an electronically active homointerface in a nonconductive material. Despite decades of research on oxide interfaces and ferroic systems, the metal-insulator transition induced solely by polarization charges without any additional chemical modification has consistently eluded the experimental realm. Here we show that a localized insulator-metal transition can be repeatedly induced within an insulating ferroelectric lead-zirconate titanate, merely by switching its polarization at the nanoscale. This surprising effect is traced to tilted boundaries of ferroelectric nanodomains, that act as localized homointerfaces within the perovskite lattice, with inherently tunable carrier density. Metallic conductance is unique to nanodomains, while the conductivity of extended domain walls and domain surfaces is thermally activated. Foreseeing future applications, we demonstrate that a continuum of nonvolatile metallic states across decades of conductance can be encoded in the size of ferroelectric nanodomains using electric field.

Topological walls separating domains of continuous polarization, magnetization, and strain in ferroic materials hold promise of novel electronic properties, that are intrinsically localized on the nanoscale and that can be patterned on demand without change of material volume or elemental composition. We have revealed that ferroelectric domain walls in multiferroic BiFeO(3) are inherently dynamic electronic conductors, closely mimicking memristive behavior and contrary to the usual assumption of rigid conductivity. Applied electric field can cause a localized transition between insulating and conducting domain walls, tune domain wall conductance by over an order of magnitude, and create a quasicontinuous spectrum of metastable conductance states. Our measurements identified that subtle and microscopically reversible distortion of the polarization structure at the domain wall is at the origin of the dynamic conductivity. The latter is therefore likely to be a universal property of topological defects in ferroelectric semiconductors.

The question of the nature and stability of polar ordering in nanoscale ferroelectrics is examined with colloidal nanocrystals of germanium telluride (GeTe). We provide atomic-scale evidence for room-temperature polar ordering in individual nanocrystals using aberration-corrected transmission electron microscopy and demonstrate a reversible, size-dependent polar-nonpolar phase transition of displacive character in nanocrystal ensembles. A substantial linear component of the distortion is observed, which is in contrast with theoretical reports predicting a toroidal state.

We demonstrate an approach to create a one-dimensional nanoscale array of domain walls in epitaxial La-substituted BiFeO(3) films. We have used a DyScO(3) (110)(O) single-crystal substrate to provide an anisotropic strain to exclude two of the possible structural variants. Furthermore, through careful control of electrostatic boundary conditions, such as the thickness of the SrRuO(3) bottom electrode to induce the self-poling effects, we can choose to obtain either 109 degrees or 71 degrees one-dimensional periodic domain walls. Detailed measurements of the domain structures is shown using piezoresponse force microscopy and X-ray diffraction, which confirms that these periodic structures are the same as those suggested in previous literature.

We demonstrate the room-temperature control of magnetization reversal with an electric field in an epitaxial nanostructure consisting of ferrimagnetic nanopillars embedded in a ferroelectric matrix. This was achieved by combining a weak, uniform magnetic field with the switching electric field to selectively switch pillars with only one magnetic configuration. On the basis of these experimental results, we propose to use an electric field to assist magnetic recording in multiferroic systems with high perpendicular magnetic anisotropy.

We present direct evidence for room-temperature magnetization reversal induced by an electric field in epitaxial ferroelectric BiFeO3-ferrimagnetic CoFe2O4 columnar nanostructures. Piezoelectric force microscopy and magnetic force microscopy were used to locally image the coupled piezoelectric-magnetic switching. Quantitative analyses give a perpendicular magnetoelectric susceptibility of approximately 1.0 x 10(-2) G cm/V. The observed effect is due to the strong elastic coupling between the two ferric constituents as the result of the three-dimensional heteroepitaxy.