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Relaxor ferroelectrics have been intensely studied for decades based on their unique electromechanical responses which arise from local structural heterogeneity involving polar nanoregions or domains. Here, we report first studies of the ultrafast dynamics and reconfigurability of the polarization in freestanding films of the prototypical relaxor 0.68PbMg

We investigate transient nanotextured heterogeneity in vanadium dioxide (VO2) thin films during a light-induced insulator-to-metal transition (IMT). Time-resolved scanning near-field optical microscopy (Tr-SNOM) is used to study VO2 across a wide parameter space of infrared frequencies, picosecond time scales, and elevated steady-state temperatures with nanoscale spatial resolution. Room temperature, steady-state, phonon enhanced nano-optical contrast reveals preexisting "hidden" disorder. The observed contrast is associated with inequivalent twin domain structures. Upon thermal or optical initiation of the IMT, coexisting metallic and insulating regions are observed. Correlations between the transient and steady-state nano-optical textures reveal that heterogeneous nucleation is partially anchored to twin domain interfaces and grain boundaries. Ultrafast nanoscopic dynamics enable quantification of the growth rate and bound the nucleation rate. Finally, we deterministically anchor photoinduced nucleation to predefined nanoscopic regions by locally enhancing the electric field of pump radiation using nanoantennas and monitor the on-demand emergent metallicity in space and time.

We investigate transient nanotextured heterogeneity in vanadium dioxide (VO

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.

Mechanical switching of ferroelectric polarization, typically realized via a scanning probe, holds promise in (multi)ferroic device applications. Whereas strain gradient-associated flexoelectricity has been regarded to be accountable for mechanical switching in ultrathin (10 nm) films, such mechanism can hardly be extended to thicker materials due to intrinsic short operating lengths of flexoelectricity. Here, we demonstrate robust mechanical switching in ∼100 nm thick Pb(Zr

Atomic layer controlled growth of epitaxial thin films of unconventional superconductors opens the opportunity to discover novel high temperature superconductors. For instance, the interfacial atomic configurations may play an important role in superconducting behavior of monolayer FeSe on SrTiO3 and other Fe-based superconducting thin films. Here, we demonstrate a selective control of the atomic configurations in Co-doped BaFe2As2 epitaxial thin films and its strong influence on superconducting transition temperatures by manipulating surface termination of (001) SrTiO3 substrates. In a combination of first-principles calculations and high-resolution scanning transmission electron microscopy imaging, we show that Co-doped BaFe2As2 on TiO2-terminated SrTiO3 is a tetragonal structure with an atomically sharp interface and with an initial Ba layer. In contrast, Co-doped BaFe2As2 on SrO-terminated SrTiO3 has a monoclinic distortion and a BaFeO3- x initial layer. Furthermore, the superconducting transition temperature of Co-doped BaFe2As2 ultrathin films on TiO2-terminated SrTiO3 is significantly higher than that on SrO-terminated SrTiO3, which we attribute to shaper interfaces with no lattice distortions. This study allows the design of the interfacial atomic configurations and the effects of the interface on superconductivity in Fe-based superconductors.

Strontium titanate (SrTiO3) is the “silicon” in the emerging field of oxide electronics. While bulk properties of this material have been studied for decades, new unexpected phenomena have recently been discovered at the nanoscale, when SrTiO3 forms an ultrathin film or an atomically sharp interface with other materials. One of the striking discoveries is room-temperature ferroelectricity in strain-free ultrathin films of SrTiO3 driven by the TiSr antisite defects, which generate a local dipole moment polarizing the surrounding nanoregion. Here, we demonstrate that these polar defects are not only responsible for ferroelectricity, but also propel the appearance of highly conductive channels, “hot spots”, in the ultrathin SrTiO3 films. Using a combination of scanning probe microscopy experimental studies and theoretical modeling, we show that the hot spots emerge due to resonant tunneling through localized electronic states created by the polar defects and that the tunneling conductance of the hot spots is...

Phase transitions in correlated materials can be manipulated at the nanoscale to yield emergent functional properties, promising new paradigms for nanoelectronics and nanophotonics. Vanadium dioxide (VO2), an archetypal correlated material, exhibits a metal–insulator transition (MIT) above room temperature. At the thicknesses required for heterostructure applications, such as an optical modulator discussed here, the strain state of VO2 largely determines the MIT dynamics critical to the device performance. We develop an approach to control the MIT dynamics in epitaxial VO2 films by employing an intermediate template layer with large lattice mismatch to relieve the interfacial lattice constraints, contrary to conventional thin film epitaxy that favors lattice match between the substrate and the growing film. A combination of phase-field simulation, in situ real-time nanoscale imaging, and electrical measurements reveals robust undisturbed MIT dynamics even at preexisting structural domain boundaries and si...

Phase transitions in 2D materials can lead to massive changes in electronic properties that enable novel electronic devices. Tantalum disulfide (TaS2), specifically the “1T” phase (1T-TaS2), exhibits a phase transition based on the formation of commensurate charge density waves (CCDW) at 180 K. In this work, we investigate the impact of substrate choice on the phase transitions in ultrathin 1T-TaS2. Doping and charge transfer from the substrate has little impact on CDW phase transitions. On the contrary, we demonstrated that substrate surface roughness is a primary extrinsic factor in CCDW transition temperature and hysteresis, where higher roughness leads to smaller transition hysteresis. Such roughness can be simulated via surface texturing of SiO2/Si substrates, which controllably and reproducibly induces periodic strain in the 1T-TaS2 and thereby enables the potential for engineering CDW phase transitions.

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

Achieving efficient spatial modulation of phonon transmission is an essential step on the path to phononic circuits using "phonon currents". With their intrinsic and reconfigurable interfaces, domain walls (DWs), ferroelectrics are alluring candidates to be harnessed as dynamic heat modulators. This paper reports the thermal conductivity of single-crystal PbTiO

Ferroelectric heterostructures, with capability of storing data at ultrahigh densities, could act as the platform for next-generation memories. The development of new device paradigms has been hampered by the long-standing notion of inevitable ferroelectricity suppression under reduced dimensions. Despite recent experimental observation of stable polarized states in ferroelectric ultrathin films, the out-of-plane polarization components in these films are strongly attenuated compared to thicker films, implying a degradation of device performance in electronic miniaturization processes. Here, in a model system of BiFeO3/La0.7Sr0.3MnO3, we report observation of a dramatic out-of-plane polarization enhancement that occurs with decreasing film thickness. Our electron microscopy analysis coupled with phase-field simulations reveals a polarization-enhancement mechanism that is dominated by the accumulation of oxygen vacancies at interfacial layers. The results shed light on the interplay between polarization and defects in nanoscale ferroelectrics and suggest a route to enhance functionality in oxide devices.

Composition gradients, or dissimilar ferroelectric bilayers, demonstrate colossal electromechanical figures of merit attributed to the motion of ferroelastic domain walls. Yet, mechanistic understanding of polarization switching pathways that drive ferroelastic switching in these systems remains elusive. Here, the crucial roles of strain and electrostatic boundary conditions in ferroelectric bilayer systems are revealed, which underpin their ferroelastic switching dynamics. Using in situ electrical biasing in the transmission electron microscope (TEM), the motion of ferroelastic domain walls is investigated in a tetragonal (T) Pb(Zr,Ti)O3 (PZT)/rhombohedral (R) PZT epitaxial bilayer system. Atomic resolution electron microscopy, in tandem with phase field simulations, indicates that ferroelastic switching is triggered by predominant nucleation at the triple domain junctions located at the interface between the T/R layers. Furthermore, this interfacial nucleation leads to systematic reversable reorientation of ferroelastic domain walls. Deterministic ferroelastic domain switching, driven by the interfacial strain and electrostatic boundary conditions in the ferroelectric bilayer, provides a viable pathway toward novel design of miniaturized energy-efficient electromechanical devices.

Magnetic domain-wall motion driven by a voltage dissipates much less heat than by a current, but none of the existing reports have achieved speeds exceeding 100 m/s. Here phase-field and finite-element simulations were combined to study the dynamics of strain-mediated voltage-driven magnetic domain-wall motion in curved nanowires. Using a ring-shaped, rough-edged magnetic nanowire on top of a piezoelectric disk, we demonstrate a fast voltage-driven magnetic domain-wall motion with average velocity up to 550 m/s, which is comparable to current-driven wall velocity. An analytical theory is derived to describe the strain dependence of average magnetic domain-wall velocity. Moreover, one 180° domain-wall cycle around the ring dissipates an ultrasmall amount of heat, as small as 0.2 fJ, approximately 3 orders of magnitude smaller than those in current-driven cases. These findings suggest a new route toward developing high-speed, low-power-dissipation domain-wall spintronics.

Atomic layer controlled growth of epitaxial thin films of unconventional superconductors opens the opportunity to discover novel high temperature superconductors. For instance, the interfacial atomic configurations may play an important role in superconducting behavior of monolayer FeSe on SrTiO

Strontium titanate (SrTiO

Substitutional doping of transition metal dichalcogenides (TMDs) may provide routes to achieving tunable p-n junctions, bandgaps, chemical sensitivity, and magnetism in these materials. In this study, we demonstrate in situ doping of monolayer molybdenum disulfide (MoS2) with manganese (Mn) via vapor phase deposition techniques. Successful incorporation of Mn in MoS2 leads to modifications of the band structure as evidenced by photoluminescence and X-ray photoelectron spectroscopy, but this is heavily dependent on the choice of substrate. We show that inert substrates (i.e., graphene) permit the incorporation of several percent Mn in MoS2, while substrates with reactive surface terminations (i.e., SiO2 and sapphire) preclude Mn incorporation and merely lead to defective MoS2. The results presented here demonstrate that tailoring the substrate surface could be the most significant factor in substitutional doping of TMDs with non-TMD elements.

Phase transitions in correlated materials can be manipulated at the nanoscale to yield emergent functional properties, promising new paradigms for nanoelectronics and nanophotonics. Vanadium dioxide (VO

The metal to insulator transition (MIT) of strongly correlated materials is subject to strong lattice coupling, which brings about the unique one-dimensional alignment of metal-insulator (M-I) domains along nanowires or nanobeams. Many studies have investigated the effects of stress on the MIT and hence the phase boundary, but few have directly examined the temperature profile across the metal-insulating interface. Here, we use thermoreflectance microscopy to create two-dimensional temperature maps of single-crystalline VO2 nanobeams under external bias in the phase coexisting regime. We directly observe highly localized alternating Peltier heating and cooling as well as Joule heating concentrated at the M-I domain boundaries, indicating the significance of the domain walls and band offsets. Utilizing the thermoreflectance technique, we are able to elucidate strain accumulation along the nanobeam and distinguish between two insulating phases of VO2 through detection of the opposite polarity of their respective thermoreflectance coefficients. Microelasticity theory was employed to predict favorable domain wall configurations, confirming the monoclinic phase identification.

A scanning probe microscopy technique for probing local ionic dynamics in electrochemically active materials based on the first-order reversal curve current-voltage (FORC-IV) method is presented. FORC-IV imaging mode is applied to a Ca-substituted bismuth ferrite (Ca-BFO) system to separate the electronic and ionic phenomena in this material and visualize the spatial variability of these behaviors. The variable-temperature measurements further demonstrate the interplay between the thermally and electric-field-driven resistance changes in Ca-BFO. The FORC-IV is shown to be a simple, powerful, and flexible method for studying electrochemical activity of materials at the nanoscale and, in conjunction with the electrochemical strain microscopy, it can be used for differentiating ferroelectric and ionic behaviors.

A new paradigm of domain wall nanoelectronics has emerged recently, in which the domain wall in a ferroic is itself an active device element. The ability to spatially modulate the ferroic order parameter within a single domain wall allows the physical properties to be tailored at will and hence opens vastly unexplored device possibilities. Here, we demonstrate via ambient and ultrahigh-vacuum (UHV) scanning probe microscopy (SPM) measurements in bismuth ferrite that the conductivity of the domain walls can be modulated by up to 500% in the spatial dimension as a function of domain wall curvature. Landau-Ginzburg-Devonshire calculations reveal the conduction is a result of carriers or vacancies migrating to neutralize the charge at the formed interface. Phase-field modeling indicates that anisotropic potential distributions can occur even for initially uncharged walls, from polarization dynamics mediated by elastic effects. These results are the first proof of concept for modulation of charge as a function of domain wall geometry by a proximal probe, thereby expanding potential applications for oxide ferroics in future nanoscale electronics.

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...

If achieved, magnetization reversal purely with an electric field has the potential to revolutionize the spintronic devices that currently utilize power-dissipating currents. However, all existing proposals involve the use of a magnetic field. Here we use phase-field simulations to study the piezoelectric and magnetoelectric responses in a three-dimensional multiferroic nanostructure consisting of a perpendicularly magnetized nanomagnet with an in-plane long axis and a juxtaposed ferroelectric nanoisland. For the first time, we demonstrate a full reversal of perpendicular magnetization via successive precession and damping, driven purely by a perpendicular electric-field pulse of certain pulse duration across the nanoferroelectric. We discuss the materials selection and size dependence of both nanoferroelctrics and nanomagnets for experimental verification. These results offer new inspiration to the design of spintronic devices that simultaneously possess high density, high thermal stability, and high reliability.

Nanocrystals (NCs) attract tremendous research interests because of their unique properties to meet the demands of functionalities. To date, hybrid NCs with multiple components are developed to meet the rising demands that could be very difficult, or even impossible to be achieved by single-component NCs. Tuning properties by strain via conjugation could be an alternative solution. Strain engineering has been discovered and widely applied to many thin-film materials for tuning physical properties. Then, there is a further question to be addressed in this study: can we take the advantages we have learned in heteroepitaxy of thin films and transfer that into the NC conjugation? In order to demonstrate this possibility, we investigated NC conjugation of BiFeO3 and LaAlO3. We found that change in either LaAlO3-NC or BiFeO3-NC size would change the stability of rhombohedral-to-tetragonal phase transition. The present results show that strain engineering is possible to be realized in not only thin film but also NC conjugation. The same concept should be applicable to other complex oxide systems in order to broaden their practical applications for the rising demands of multifunctionalities.