Effect of sub-micron grains and defect-dipole interactions on dielectric properties of iron, cobalt, and copper doped barium titanate ceramics.

Introduction: Dilutely doped ferroelectric materials are of interest, as engineering these materials by introducing point defects via doping often leads to unique behavior not otherwise achievable in the undoped material. For example, B-site doping with transition metals in barium titanate (BaTiO3, or BTO) creates defect dipoles via oxygen vacancies leading enhanced polarization, strain, and the ability to tune dielectric properties. Though defect dipoles should lead to dielectric property enhancements, the effect of grain size in polycrystalline ferroelectrics such as BTO plays a significant role in those properties as well. Methods: Herein, doped BTO with 1.0% copper (Cu), iron (Fe), or cobalt (Co) was synthesized using traditional solid-state processing to observe the contribution of both defect-dipole formation and grain size on the ferroelectric and dielectric properties. Results and discussion: 1.0% Cu doped BTO showed the highest polarization and strain (9.3 µC/cm2 and 0.1%, respectively) of the three doped BTO samples. While some results, such as the aforementioned electrical properties of the 1.0% Cu doped BTO can be explained by the strong chemical driving force of the Cu atoms to form defect dipoles with oxygen vacancies and copper's consistent +2 valency leading to stable defect-dipole formation (versus the readily mixed valency states of Fe and Co at +2/+3), other properties cannot. For instance, all three Tc values should fall below that of undoped BTO (typically 120°C-135°C), but the Tc of 1.0% Cu BTO actually exceeds that range (139.4°C). Data presented on the average grain size and distribution of grain sizes provides insight allowing us to decouple the effect of defect dipoles and the effect of grain size on properties such as Tc, where the 1.0% Cu BTO was shown to possess the largest overall grains, leading to its increase in Tc. Conclusion/future work: Overall, the 1% Cu BTO possessed the highest polarization, strain, and Tc and is a promising dopant for engineering the performance of the material. This work emphasizes the challenge of extricating one effect (such as defect-dipole formation) from another (grain size modification) inherent to doping polycrystalline BTO.

High Isolation, Double-Clamped, Magnetoelectric Microelectromechanical Resonator Magnetometer.

Magnetoelectric (ME)-based magnetometers have garnered much attention as they boast ultra-low-power systems with a small form factor and limit of detection in the tens of picotesla. The highly sensitive and low-power electric readout from the ME sensor makes them attractive for near DC and low-frequency AC magnetic fields as platforms for continuous magnetic signature monitoring. Among multiple configurations of the current ME magnetic sensors, most rely on exploiting the mechanically resonant characteristics of a released ME microelectromechanical system (MEMS) in a heterostructure device. Through optimizing the resonant device configuration, we design and fabricate a fixed-fixed resonant beam structure with high isolation compared to previous designs operating at ~800 nW of power comprised of piezoelectric aluminum nitride (AlN) and magnetostrictive (Co1-xFex)-based thin films that are less susceptible to vibration while providing similar characteristics to ME-MEMS cantilever devices. In this new design of double-clamped magnetoelectric MEMS resonators, we have also utilized thin films of a new iron-cobalt-hafnium alloy (Fe0.5Co0.5)0.92Hf0.08 that provides a low-stress, high magnetostrictive material with an amorphous crystalline structure and ultra-low magnetocrystalline anisotropy. Together, the improvements of this sensor design yield a magnetic field sensitivity of 125 Hz/mT when released in a compressive state. The overall detection limit of these sensors using an electric field drive and readout are presented, and noise sources are discussed. Based on these results, design parameters for future ME MEMS field sensors are discussed.

Enhancing Converse Magnetoelectric Coupling Through Strain Engineering in Artificial Multiferroic Heterostructures.

Magnetoelectric materials present a unique opportunity for electric field-controlled magnetism. Even though strain-mediated multiferroic heterostructures have shown unprecedented increase in magnetoelectric coupling compared to single-phase materials, further improvements must be made before ultra-low power memory, logic, magnetic sensors, and wide spectrum antennas can be realized. This work presents how magnetoelectric coupling can be enhanced by simultaneously exploiting multiple strain engineering approaches in heterostructures composed of Fe0.5Co0.5/Ag multilayers on (011) Pb(In1/2Nb1/2)O3-Pb(Mg1/3Nb2/3)O3-PbTiO3 piezoelectric crystals. When grown and measured under strain, these heterostructures exhibit an effective converse magnetoelectric coefficient in the order of 10-5 s m-1: the highest directly measured, non-resonant value to-date. This response occurred at room temperature and at low electric fields (<2 kV cm-1). This large effect is enabled by magnetization reorientation caused by changing the magnetic anisotropy with strain from the substrate and the use of multilayered magnetic materials to minimize the internal stress from deposition. Additionally, the coercive field dependence of the magnetoelectric response under strain suggests contributions from domain-mediated magnetization switching modified by voltage-induced magnetoelastic anisotropy. This work highlights how multicomponent strain engineering enables enhanced magnetoelectric coupling in heterostructures and provides an approach to realize energy-efficient magnetoelectric applications.

Simultaneous Large Optical and Piezoelectric Effects Induced by Domain Reconfiguration Related to Ferroelectric Phase Transitions.

Electrical switching of ferroelectric domains and subsequent domain wall motion promotes strong piezoelectric activity, however, light scatters at refractive index discontinuities such as those found at domain wall boundaries. Thus, simultaneously achieving large piezoelectric effect and high optical transmissivity is generally deemed infeasible. Here, it is demonstrated that the ferroelectric domains in perovskite Pb(In1/2 Nb1/2 )O3 -Pb(Mg1/3 Nb2/3 )O3 -PbTiO3 domain-engineered crystals can be manipulated by electrical field and mechanical stress to reversibly and repeatably, with small hysteresis, transform the opaque polydomain structure into a highly transparent monodomain state. This control of optical properties can be achieved at very low electric fields (less than 1.5 kV cm-1 ) and is accompanied by a large (>10 000 pm V-1 ) piezoelectric coefficient that is superior to linear state-of-the-art materials by a factor of three or more. The coexistence of tunable optical transmissivity and high piezoelectricity paves the way for a new class of photonic devices.

Ultra-low-field magneto-elastocaloric cooling in a multiferroic composite device.

The advent of caloric materials for magnetocaloric, electrocaloric, and elastocaloric cooling is changing the landscape of solid state cooling technologies with potentials for high-efficiency and environmentally friendly residential and commercial cooling and heat-pumping applications. Given that caloric materials are ferroic materials that undergo first (or second) order phase transitions near room temperature, they open up intriguing possibilities for multiferroic devices with hitherto unexplored functionalities coupling their thermal properties with different fields (magnetic, electric, and stress) through composite configurations. Here we demonstrate a magneto-elastocaloric effect with ultra-low magnetic field (0.16 T) in a compact geometry to generate a cooling temperature change as large as 4 K using a magnetostriction/superelastic alloy composite. Such composite systems can be used to circumvent shortcomings of existing technologies such as the need for high-stress actuation mechanism for elastocaloric materials and the high magnetic field requirement of magnetocaloric materials, while enabling new applications such as compact remote cooling devices.

Large Interfacial Magnetostriction in (Co/Ni)4/Pb(Mg1/3Nb2/3)O3-PbTiO3 Multiferroic Heterostructures.

The magnetoelastic behavior of multiferroic heterostructures-coupling of magnetic anisotropy or domain dynamics to structural deformations-has been intensively studied for developing materials for energy-efficient, spin-based applications. Here, we report on a large, interface-dominated magnetostriction in (Co/Ni)4/Pb(Mg1/3Nb2/3)O3-PbTiO3 multiferroic heterostructures. Ferromagnetic resonance spectroscopy under voltage-induced strains enabled estimation of the saturation magnetostriction as a function of Ni thickness. The volume and the interface components to the saturation magnetostriction are (6.6 ± 0.9) × 10-6 and (-2.2 ± 0.2) × 10-14 m, respectively. Similar to perpendicular magnetic anisotropy in Co/Ni, the large, negative magnetostriction originates from the Co/Ni interfaces. This interfacial functionality delivers an effect over 300% larger than the bulk contribution and can enable low-energy, nanoelectronic devices that combine the tunable magnetic and magnetostrictive properties of Co/Ni multilayers with the ferroelectric properties of Pb(Mg1/3Nb2/3)O3-PbTiO3.

Reversible strain control of magnetic anisotropy in magnetoelectric heterostructures at room temperature.

The ability to tune both magnetic and electric properties in magnetoelectric (ME) composite heterostructures is crucial for multiple transduction applications including energy harvesting or magnetic field sensing, or other transduction devices. While large ME coupling achieved through interfacial strain-induced rotation of magnetic anisotropy in magnetostrictive/piezoelectric multiferroic heterostructures has been demonstrated, there are presently certain restrictions for achieving a full control of magnetism in an extensive operational dynamic range, limiting practical realization of this effect. Here, we demonstrate the possibility of generating substantial reversible anisotropy changes through induced interfacial strains driven by applied electric fields in magnetostrictive thin films deposited on (0 1 1)-oriented domain-engineered ternary relaxor ferroelectric single crystals with extended temperature and voltage ranges as compared to binary relaxors. We show, through a combination of angular magnetization and magneto-optical domain imaging measurements, that a 90° in-plane rotation of the magnetic anisotropy and propagation of magnetic domains with low applied electric fields under zero electric field bias are realized. To our knowledge, the present value attained for converse magnetoelectric coupling coefficient is the highest achieved in the linear piezoelectric regime and expected to be stable for a wide temperature range, thus representing a step towards practical ME transduction devices.