Large-scale multiferroic complex oxide epitaxy with magnetically switched polarization enabled by solution processing.

Complex oxides with tunable structures have many fascinating properties, though high-quality complex oxide epitaxy with precisely controlled composition is still out of reach. Here we have successfully developed solution-based single-crystalline epitaxy for multiferroic (1-x)BiTi(1-y)/2Fe y Mg(1-y)/2O3-(x)CaTiO3 (BTFM-CTO) solid solution in large area, confirming its ferroelectricity at the atomic scale with strong spontaneous polarization. Careful compositional tuning leads to a bulk magnetization of 0.07 ± 0.035 µB/Fe at room temperature, enabling magnetically induced polarization switching exhibiting a large magnetoelectric coefficient of 2.7-3.0 × 10-7 s/m. This work demonstrates the great potential of solution processing in large-scale complex oxide epitaxy and establishes novel room-temperature magnetoelectric coupling in epitaxial BTFM-CTO film, making it possible to explore a much wider space of composition, phase, and structure that can be easily scaled up for industrial applications.

Super-elastic ferroelectric single-crystal membrane with continuous electric dipole rotation.

Ferroelectrics are usually inflexible oxides that undergo brittle deformation. We synthesized freestanding single-crystalline ferroelectric barium titanate (BaTiO3) membranes with a damage-free lifting-off process. Our BaTiO3 membranes can undergo a ~180° folding during an in situ bending test, demonstrating a super-elasticity and ultraflexibility. We found that the origin of the super-elasticity was from the dynamic evolution of ferroelectric nanodomains. High stresses modulate the energy landscape markedly and allow the dipoles to rotate continuously between the a and c nanodomains. A continuous transition zone is formed to accommodate the variant strain and avoid high mismatch stress that usually causes fracture. The phenomenon should be possible in other ferroelectrics systems through domain engineering. The ultraflexible epitaxial ferroelectric membranes could enable many applications such as flexible sensors, memories, and electronic skins.

Electrically Driven Reversible Magnetic Rotation in Nanoscale Multiferroic Heterostructures.

Electrically driven magnetic switching (EDMS) is highly demanded for next-generation advanced memories or spintronic devices. The key challenge is to achieve repeatable and reversible EDMS at sufficiently small scale. In this work, we reported an experimental realization of room-temperature, electrically driven, reversible, and robust 120° magnetic state rotation in nanoscale multiferroic heterostructures consisting of a triangular Co nanomagnet array on tetragonal BiFeO3 films, which can be directly monitored by magnetic force microscope (MFM) imaging. The observed reversible magnetic switching in an individual nanomagnet can be triggered by a small electric pulse within 10 V with an ultrashort time of ∼10 ns, which also demonstrates sufficient switching cycling and months-long retention lifetime. A mechanism based on synergic effects of interfacial strain and exchange coupling plus shape anisotropy was also proposed, which was also verified by micromagnetic simulations. Our results create an avenue to engineer the nanoscale EDMS for low-power-consumption, high-density, nonvolatile magnetoelectric memories and beyond.

Multifield Control of Domains in a Room-Temperature Multiferroic 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 Thin Film.

Single-phase materials that combine electric polarization and magnetization are promising for applications in multifunctional sensors, information storage, spintronic devices, etc. Following the idea of a percolating network of magnetic ions (e.g., Fe) with strong superexchange interactions within a structural scaffold with a polar lattice, a solid solution thin film with perovskite structure at a morphotropic phase boundary with a high level of Fe atoms on the B site of perovskite structure is deposited to combine both ferroelectric and ferromagnetic ordering at room temperature with magnetoelectric coupling. In this work, a 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 thin film has been deposited by pulsed laser deposition (PLD). Both the ferroelectricity and the magnetism were characterized at room temperature. Large polarization and a large piezoelectric effective coefficient d33 were obtained. Multifield coupling of the thin film has been characterized by scanning force microscopy. Ferroelectric domains and magnetic domains could be switched by magnetic field ( H), electric field ( E), mechanical force ( F), and, indicating that complex cross-coupling exists among the electric polarization, magnetic ordering and elastic deformation in 0.85BiTi0.1Fe0.8Mg0.1O3-0.15CaTiO3 thin film at room temperature. This work also shows the possibility of writing information with electric field, magnetic field, and mechanical force and then reading data by magnetic field. We expect that this work will benefit information applications.

High-density array of ferroelectric nanodots with robust and reversibly switchable topological domain states.

The exotic topological domains in ferroelectrics and multiferroics have attracted extensive interest in recent years due to their novel functionalities and potential applications in nanoelectronic devices. One of the key challenges for these applications is a realization of robust yet reversibly switchable nanoscale topological domain states with high density, wherein spontaneous topological structures can be individually addressed and controlled. This has been accomplished in our work using high-density arrays of epitaxial BiFeO3 (BFO) ferroelectric nanodots with a lateral size as small as ~60 nm. We demonstrate various types of spontaneous topological domain structures, including center-convergent domains, center-divergent domains, and double-center domains, which are stable over sufficiently long time but can be manipulated and reversibly switched by electric field. The formation mechanisms of these topological domain states, assisted by the accumulation of compensating charges on the surface, have also been revealed. These results demonstrated that these reversibly switchable topological domain arrays are promising for applications in high-density nanoferroelectric devices such as nonvolatile memories.

Fabrication of high-density BiFeO3 nanodot and anti-nanodot arrays by anodic alumina template-assisted ion beam etching.

Efficient and cost-competitive fabrication of high-quality ferroelectric and multiferroic nanostructures is of general interest. In this work, a top-down nano-patterning technique is developed by the Ar+ ion beam etching in combination with the sacrificed ultrathin anodic alumina (AAO) mask. This technique is demonstrated by preparation of the epitaxial BiFeO3 (BFO) nanostructures of various geometries, including nanodot and anti-nanodot arrays. The lateral dot size is as small as ∼60 nm and an ultrahigh dot density of ∼60 Gbit/inch2 is achieved. It is revealed that the etching process involves sequential shape evolution of both the AAO mask and the underlying BFO film, resulting in the nanodots and anti-nanodots arrays of various geometries. The as-etched BFO nanodots array exhibits well-established ferroelectric domain structures and reversible polarization switching, as examined by piezoresponse force microscopy (PFM). It is suggested that this technique is extendable to fabrication of a wide range of functional oxide nanostructures for potential nanoelectronic applications.

Magnetoelectric Coupling in Well-Ordered Epitaxial BiFeO3/CoFe2O4/SrRuO3 Heterostructured Nanodot Array.

Multiferroic magnetoelectric (ME) composites exhibit sizable ME coupling at room temperature, promising applications in a wide range of novel devices. For high density integrated devices, it is indispensable to achieve a well-ordered nanostructured array with reasonable ME coupling. For this purpose, we explored the well-ordered array of isolated epitaxial BiFeO3/CoFe2O4/SrRuO3 heterostructured nanodots fabricated by nanoporous anodic alumina (AAO) template method. The arrayed heterostructured nanodots demonstrate well-established epitaxial structures and coexistence of piezoelectric and ferromagnetic properties, as revealed by transmission electron microscopy (TEM) and peizoeresponse/magnetic force microscopy (PFM/MFM). It was found that the heterostructured nanodots yield apparent ME coupling, likely due to the effective transfer of interface couplings along with the substantial release of substrate clamping. A noticeable change in piezoelectric response of the nanodots can be triggered by magnetic field, indicating a substantial enhancement of ME coupling. Moreover, an electric field induced magnetization switching in these nanodots can be observed, showing a large reverse ME effect. These results offer good opportunities of the nanodots for applications in high-density ME devices, e.g., high density recording (>100 Gbit/in.(2)) or logic devices.