Multiferroics have received a great deal of attention because of their fascinating physics of order-parameter cross-couplings and their potential for enabling new device paradigms. Considering the rareness of multiferroic materials, we have been exploring the possibility of artificially imposing ferroelectricity by structurally tailoring antiferromagnets in thin-film forms. YbFeO(3) (YbFO hereafter), a family of centrosymmetric rare-earth orthoferrites, is known to be nonferroelectric (space group Pnma). Here we report that a YbFO thin-film heterostructure fabricated by adopting a hexagonal template surprisingly exhibits nonferroelastic ferroelectricity with the Curie temperature of 470 K. The observed ferroelectricity is further characterized by an extraordinary two-step polarization decay, accompanied by a pronounced magnetocapacitance effect near the lower decay temperature, ~225 K. According to first-principles calculations, the hexagonal P6(3)/mmc-P6(3)mc-P6(3)cm consecutive transitions are primarily responsible for the observed two-step polarization decay, and the ferroelectricity originates from the c-axis-oriented asymmetric Yb 5d(z(2))-O 2p(z) orbital hybridization. Temperature-dependent magnetization curves further reveal an interesting phenomenon of spontaneous magnetization reversal at 83 K, which is attributed to the competition between two distinct magnetocrystalline anisotropy terms, Fe 3d and Yb 4f moments.

Ferroelectric photovoltaics (FPVs) have drawn much attention owing to their high stability, environmental safety, anomalously high photovoltages, coupled with reversibly switchable photovoltaic responses. However, FPVs suffer from extremely low photocurrents, which is primarily due to their wide band gaps. Here, we present a new class of FPVs by demonstrating switchable ferroelectric photovoltaic effects using hexagonal ferrite (h-RFeO3) thin films having narrow band gaps of ~1.2 eV, where R denotes rare-earth ions. FPVs with narrow band gaps suggests their potential applicability as photovoltaic and optoelectronic devices. The h-RFeO3 films further exhibit reasonably large ferroelectric polarizations (4.7~8.5 μC•cm -2 ), which possibly reduces a rapid recombination rate of the photo-generated electron-hole pairs.The power conversion efficiency (PCE) of h-RFeO3 thin-film devices is sensitive on the magnitude of polarization. In the case of h-TmFeO3 (h-TFO) thin film, the measured PCE is twice as large as that of the BiFeO3 thin film, a prototypic FPV. We have further shown that the switchable photovoltaic effect dominates over the unswitchable internal field effect arising from the net built-in potential. This work thus demonstrates a new class of FPVs towards highefficiency solar cell and optoelectronic applications.

Orthorhombic GaFeO 3 (o-GFO) with the polar Pna2 1 space group is a prominent ferrite owing to its piezoelectricity and ferrimagnetism, coupled with magnetoelectric effects. Herein, we demonstrate large ferroelectric remanent polarization in undoped o-GFO thin films by adopting either a hexagonal strontium titanate (STO) or a cubic yttrium-stabilized zirconia (YSZ) substrate. The polarization-electric-field hysteresis curves of the polar c-axis-grown o-GFO film on a SrRuO 3 /STO substrate show the net switching polarization of~35 μC cm − 2 with an unusually high coercive field (E c ) of ± 1400 kV cm − 1 at room temperature. The positive-up and negative-down measurement also demonstrates the switching polarization of~26 μC cm − 2 . The activation energy for the polarization switching, as obtained by density-functional theory calculations, is remarkably high, 1.05 eV per formula unit. We have theoretically shown that this high value accounts for the extraordinary high E c and the stability of the polar Pna2 1 phase over a wide range of temperatures up to 1368 K.

We propose a recently discovered material, namely, β-CuGaO2 [T. Omata et al., J. Am. Chem. Soc. 2014, 136, 3378] as a strong candidate material for efficient ferroelectric photovoltaics (FPVs). According to first-principles predictions exploiting hybrid density functional, β-CuGaO2 is ferroelectric with a remarkably large remanent polarization of 83.80 μC/cm2, even exceeding that of the prototypic FPV material, BiFeO3. Quantitative theoretical analysis further indicates the asymmetric Ga 3d z 2 –O 2p z hybridization as the origin of the Pna21 ferroelectricity. In addition to the large displacive polarization, unusually small band gap (1.47 eV) and resultantly strong optical absorptions additionally differentiate β-CuGaO2 from conventional ferroelectrics; this material is expected to overcome critical limitations of currently available FPVs.

Multiferroics that show simultaneous ferroic responses have received a great deal of attention by virtue of their potential for enabling new device paradigms. Here, we demonstrate a high-density four-states multiferroic memory using vertically aligned Mn-doped BaTiO3 nanorods prepared by applying the dip-pen nanolithography technique. In the present nanorods array, the polarization (P) switching by an external electric field does not influence the magnetization (M) of the nanorod owing to a negligible degree of the P-M cross-coupling. Similarly, the magnetic-field-induced M switching is unaffected by the ferroelectric polarization. On the basis of these, we are able to implement a four-states nonvolatile multiferroic memory, namely, (+P,+M), (+P,-M) ,(-P,+M), and (-P,-M) with the reliability in the P and M switching. Thus, the present work makes an important step toward the practical realization of multistate ferroic memories.