Magnetoelectric coupling in multiferroics probed by optical second harmonic generation.

Magnetoelectric coupling, as a fundamental physical nature and with the potential to add functionality to devices while also reducing energy consumption, has been challenging to be probed in freestanding membranes or two-dimensional materials due to their instability and fragility. In this paper, we report a magnetoelectric coupling probed by optical second harmonic generation with external magnetic field, and show the manipulation of the ferroelectric and antiferromagnetic orders by the magnetic and thermal fields in BiFeO3 films epitaxially grown on the substrates and in the freestanding ones. Here we define an optical magnetoelectric-coupling constant, denoting the ability of controlling light-induced nonlinear polarization by the magnetic field, and found the magnetoelectric-coupling was suppressed by strain releasing but remain robust against thermal fluctuation for freestanding BiFeO3.

Ferroelectric Single-Molecule Magnet with Toroidal Magnetic Moments.

Materials that coexist magnetic and electric properties on the molecular scale in single-molecule magnets (SMMs) with peculiar quantum behaviors have promise in molecular electronics and spintronics. Nevertheless, such molecular materials are limited in potentials because their magnetic signal cannot be transformed into an electrical signal through magnetoresistance or Hall effects for their high insulativity. The discovery of an entirely new material, ferroelectric SMMs (FE SMMs) is reported. This FE SMM also shows single-molecule magnetic behaviors, toroidal magnetic moments, and room-temperature ferroelectricity. The toroidal moment is formed by a vortex distribution of magnetic dipoles in triangular Dy3 clusters. The analysis of ac magnetic susceptibility reveals the coexistence of three distinct magnetic relaxation processes at low temperatures. The ferroelectricity is introduced by incorporating polar alcohol molecules in the structure, which is confirmed by the X-ray diffraction and optical second harmonic generation (SHG) measurements. Moreover, the dielectric measurements reveal a ferroelectric-to-ferroelectric phase transition around 150 K due to the symmetry change from Pc to Pna21 . The coexistence of toroidal moment and ferroelectricity along with quantum magnetism in the rare-earth single-molecule magnets yields a unique class of multiferroics.

Tunable electronic structure and magnetic anisotropy in bilayer ferromagnetic semiconductor Cr2Ge2Te6.

The emergence of ferromagnetism in two-dimensional van der Waals materials has aroused broad interest. However, the ferromagnetic instability has been a problem remained. In this work, by using the first-principles calculations, we identified the critical ranges of strain and doping for the bilayer Cr2Ge2Te6 within which the ferromagnetic stability can be enhanced. Beyond the critical range, the tensile strain can induce the phase transition from the ferromagnetic to the antiferromagnetic, and the direction of magnetic easy axis can be converted from out-of-plane to in-plane due to the increase of compressive strain, or electrostatic doping. We also predicted an electron doping range, within which the ferromagnetism can be enhanced, while the ferromagnetic stability was maintained. Moreover, we found that the compressive strain can reverse the spin polarization of electrons at the conduction band minimum, so that two categories of half-metal can be induced by controlling electrostatic doping in the bilayer Cr2Ge2Te6. These results should shed a light on achieving ferromagnetic stability for low-dimensional materials.

Improper molecular ferroelectrics with simultaneous ultrahigh pyroelectricity and figures of merit.

Although ferroelectric materials exhibit large pyroelectric coefficients, their pyroelectric figures of merit (FOMs) are severely limited by their high dielectric constants because of the inverse relationship between FOMs and dielectric constant. Here, we report the molecular ferroelectric [Hdabco]ClO4 and [Hdabco]BF4 (dabco = diazabicyclo[2.2.2]octane) exhibiting improper ferroelectric behavior and pyroelectric FOMs outperforming the current ferroelectrics. Concurrently, the improper molecular ferroelectrics have pyroelectric coefficients that are more than one order of magnitude greater than the state-of-the-art pyroelectric Pb(Mg1/3Nb2/3)O3-PbTiO3 Our first-principles and thermodynamic calculations show that the strong coupling between the order parameters, i.e., the rotation angle of anions and polarization, is responsible for the colossal pyroelectric coefficient of the molecular ferroelectrics. Along with the facile preparation and self-poling features, the improper molecular ferroelectrics hold great promise for high-performance pyroelectric devices.

Strong Ferromagnetism Achieved via Breathing Lattices in Atomically Thin Cobaltites.

Low-dimensional quantum materials that remain strongly ferromagnetic down to monolayer thickness are highly desired for spintronic applications. Although oxide materials are important candidates for the next generation of spintronics, ferromagnetism decays severely when the thickness is scaled to the nanometer regime, leading to deterioration of device performance. Here, a methodology is reported for maintaining strong ferromagnetism in insulating LaCoO3 (LCO) layers down to the thickness of a single unit cell. It is found that the magnetic and electronic states of LCO are linked intimately to the structural parameters of adjacent "breathing lattice" SrCuO2 (SCO). As the dimensionality of SCO is reduced, the lattice constant elongates over 10% along the growth direction, leading to a significant distortion of the CoO6 octahedra, and promoting a higher spin state and long-range spin ordering. For atomically thin LCO layers, surprisingly large magnetic moment (0.5 µB /Co) and Curie temperature (75 K), values larger than previously reported for any monolayer oxides are observed. The results demonstrate a strategy for creating ultrathin ferromagnetic oxides by exploiting atomic heterointerface engineering, confinement-driven structural transformation, and spin-lattice entanglement in strongly correlated materials.

Manipulating the Ferroelectric Domain States and Structural Distortion in Epitaxial BiFeO3 Ultrathin Films via Bi Nonstoichiometry.

Exploring and manipulating domain configurations in ferroelectric thin films are of critical importance for the design and fabrication of ferroelectric heterostructures with a novel functional performance. In this study, BiFeO3 (BFO) ultrathin films with various Bi/Fe ratios from excess Bi to deficient Bi have been grown on (La0.7Sr0.3)MnO3 (LSMO)-covered SrTiO3 substrates by a laser molecular beam epitaxy system. Atomic force microscopy and piezoresponse force microscopy measurements show that both the surface morphology and ferroelectric polarization of the films are relevant to Bi nonstoichiometry. More significantly, a Bi-excess thin film shows an upward (from substrate to film surface) uniform ferroelectric polarization, whereas a Bi-deficient thin film exhibits a downward uniform polarization, which means the as-grown polarization of BFO thin films can be controlled by changing the Bi contents. Atomic-scale structural and chemical characterizations and second-harmonic generation measurements reveal that two different kinds of structural distortions and interface atomic configurations in the BFO/LSMO heterostructures can be induced by the change of Bi nonstoichiometry, leading to the two opposite as-grown ferroelectric polarizations. It has also been revealed that the band gap of BFO thin films can be modulated via Bi nonstoichiometry. These results demonstrate that Bi nonstoichiometry plays a key role on the ferroelectric domain states and physical properties of BFO thin films and also open a new avenue to manipulate the structure and ferroelectric domain states in BFO thin films.

Direct evidence of correlation between the second harmonic generation anisotropy patterns and the polarization orientation of perovskite ferroelectric.

For ferroelectric materials, where the polar state breaks the inversion symmetry, second harmonic generation is a useful tool to prove their ferroelectric properties. However, the correlation between the anisotropy patterns and the polarization orientation of the ferroelectric domains has not been clarified yet. In this work, we systematically investigated this correlation in a typical perovskite oxide ferroelectric, Barium Titanate (BaTiO3) crystal, by second harmonic generation and the piezoresponse force microscopy technique. The evolution of polarization-dependent anisotropy patterns proves that there is a linear relationship between the rotation angle of second harmonic generation anisotropy patterns and the polarization angle of BaTiO3 single crystals. It is a direct evidence illustrating that the polarization of BaTiO3 crystal can be qualitatively identified in 0°-180° by second harmonic generation technology. This work gives a glance at improving a nonintrusive and convenient method to identify the polarization of perovskite ferroelectric materials.

Manipulating magnetoelectric properties by interfacial coupling in La0.3Sr0.7MnO3/Ba0.7Sr0.3TiO3 superlattices.

Artificial superlattices constructed with ferromagnetic La0.7Sr0.3MnO3 layer and ferroelectric Ba0.7Sr0.3TiO3 layer were designed and fabricated on SrTiO3 substrates. An epitaxial growth with sharp interfaces between La0.7Sr0.3MnO3 and Ba0.7Sr0.3TiO3 layers was confirmed by scanning transmission electron microscopy and x-ray diffraction. An unambiguous charge transfer involving an electron transferring from the La0.7Sr0.3MnO3 layers to Ba0.7Sr0.3TiO3 layers (Mn3+→Mn4+; Ti4+→Ti3+) across the interface were resolved by electron energy loss spectra analysis. These observations are attributed to the possible modification in the stereochemistry of the Ti and Mn ions in the interfacial region. The out-of-plane lattice parameter, Curie temperature, and magnetoresistance are strongly affected by the thicknesses of the La0.7Sr0.3MnO3 and Ba0.7Sr0.3TiO3 layers. Huge magnetoresistance subsisting to low temperature was also observed in the La0.7Sr0.3MnO3/Ba0.7Sr0.3TiO3 superlattices. All spectral changes identified at a nanometer scale and their potential effect on the degradation of magnetic and transport properties at a macroscopic level. These findings highlight the importance of dependence on sublayer thickness, illustrating the high degree of tenability in these artificially low-dimensional oxide materials.

Evolution of structural distortion in BiFeO3 thin films probed by second-harmonic generation.

BiFeO3 thin films have drawn much attention due to its potential applications for novel magnetoelectric devices and fundamental physics in magnetoelectric coupling. However, the structural evolution of BiFeO3 films with thickness remains controversial. Here we use an optical second-harmonic generation technique to explore the phase-related symmetry evolution of BiFeO3 thin films with the variation of thickness. The crystalline structures for 60 and 180-nm-thick BiFeO3 thin films were characterized by high-resolution X-ray diffractometry reciprocal space mapping and the local piezoelectric response for 60-nm-thick BiFeO3 thin films was characterized by piezoresponse force microscopy. The present results show that the symmetry of BiFeO3 thin films with a thickness below 60 nm belongs to the point group 4 mm. We conclude that the disappearance of fourfold rotational symmetry in SHG s-out pattern implies for the appearance of R-phase. The fact that the thinner the film is, the closer to 1 the tensor element ratio χ31/χ15 tends, indicates an increase of symmetry with the decrease of thickness for BiFeO3 thin films.