Recently, ferroelectric perovskite oxides have drawn much attention due to potential applications in the field of solar energy conversion. However, the power conversion efficiency of ferroelectric photovoltaic effect currently reported is far below the expectable value. One of the crucial problems lies in the two back-to-back Schottky barriers, which are formed at the ferroelectric-electrode interfaces and blocking most of photo-generated carriers to reach the outside circuit. Herein, we develop a new approach to enhance the ferroelectric photovoltaic effect by introducing the polarization-dependent interfacial coupling effect. Through inserting a semiconductor ZnO layer with spontaneous polarization into the ferroelectric ITO/PZT/Au film, a p-n junction with strong polarization-dependent interfacial coupling effect is formed. The power conversion efficiency of the heterostructure is improved by nearly two orders of magnitude and the polarization modulation ratio is increased about four times. It is demonstrated that the polarization-dependent interfacial coupling effect can give rise to a great change in band structure of the heterostructure, not only producing an aligned internal electric field but also tuning both depletion layer width and potential barrier height at PZT-ZnO interface. This work provides an efficient way in developing highly efficient ferroelectric-based solar cells and novel optoelectronic memory devices.
Polycrystalline BiFe0.9Mn0.1O3 thin films have been prepared on Pt/Ti/SiO2/Si wafers by a sol-gel process. The film exhibits typical resistive switching (RS) effect. Moreover, accompanied with the RS process, remarkable magnetization switching (MS) behaviors happen, i.e., at low resistance state the film shows high saturation magnetization, while showing low saturation magnetization at high resistance state. We revealed that such a MS effect mainly originates from the conversion of Fe ion valence state between Fe2+ and Fe3+ during the RS process, which was confirmed by the x-ray photoelectron spectroscopy measurements. The further first-principle calculations showed that the doping of Mn into the BiFeO3 could induce an impurity energy level which makes it facile to achieve the conversion of Fe ion valence state. Based on the conductive filament model, a possible mechanism of tuning the MS effect by RS process is proposed, which is closely related to the conversion of Fe ion valence state along with the forming and rupture of conduction filaments. This work provides us a promising avenue to design switchable multistate devices with both electric and magnetic functionalities.
The 0–3 type CoFe2O4-Pb(Zr,Ti)O3 (CFO-PZT) multiferroic composite films have been prepared by a sol-gel process and spin-coating technique. A confirmable photovoltaic effect is observed under ultraviolet light irradiation. Moreover, this photovoltaic effect can be tuned by external magnetic fields. The maximum magnetic modulation ratios of short-circuit current density and open-circuit voltage can reach as high as 13.7% and 12.8% upon the application of 6 kOe DC magnetic field. Through remnant polarization measurements under various magnetic fields and detailed analysis of the energy band structures, we elucidate the mechanism of tuning photovoltaic effect by magnetic fields and attribute it to the combination of two factors. One is the decreased ferroelectric-polarization-induced depolarization electric field and another is the band structure reconstruction at CFO-PZT interfaces, both of which are dominated by the magnetoelectric coupling via interfacial stress transferring at nanoscale. This work makes some attempts of coupling photo-induced effects with magnetoelectric effect in multiferroic materials and will widen the practical ranges of multiferroic-based applications.
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