No Arabic abstract
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, 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 high-efficiency solar cell and optoelectronic applications.
We report on multiple fundamental qualitative improvements in the growth of improper ferroelectric hexagonal YMnO$_3$ (YMO) thin films and heterostructures by pulsed laser deposition (PLD). By a combination of pre-growth substrate annealing and low-energy-fluence PLD, we obtain a two-dimensional growth mode of the YMO films on yttria-stabilized zirconia (YSZ) with ultralow roughness and devoid of misoriented nanocrystalline inclusions. By inserting a sacrificial manganite layer capped with conducting indium-tin oxide between the substrate and the final film, the latter is grown in a fully lattice-relaxed mode and, thus, without any misfit dislocations while maintaining the extraordinary flatness of the films grown directly on pre-annealed YSZ. This provides a template for the fabrication of heterostructures based on hexagonal manganites as promising class of multiferroics with improper room-temperature ferroelectricity and the implementation of these into technologically relevant epitaxial metal|ferroelectric-type multilayers.
We report on nanoscale strain gradients in ferroelectric HoMnO3 epitaxial thin films, resulting in a giant flexoelectric effect. Using grazing-incidence in-plane X-ray diffraction, we measured strain gradients in the films, which were 6 or 7 orders of magnitude larger than typical values reported for bulk oxides. The combination of transmission electron microscopy, electrical measurements, and electrostatic calculations showed that flexoelectricity provides a means of tuning the physical properties of ferroelectric epitaxial thin films, such as domain configurations and hysteresis curves.
Doping ferroelectric Hf0.5Zr0.5O2 with La is a promising route to improve endurance. However, the beneficial effect of La on the endurance of polycrystalline films may be accompanied by degradation of the retention. We have investigated the endurance - retention dilemma in La-doped epitaxial films. Compared to undoped epitaxial films, large values of polarization are obtained in a wider thickness range, whereas the coercive fields are similar, and the leakage current is substantially reduced. Compared to polycrystalline La-doped films, epitaxial La-doped films show more fatigue but there is not significant wake-up effect and endurance-retention dilemma. The persistent wake-up effect common to polycrystalline La-doped Hf0.5Zr0.5O2 films, is limited to a few cycles in epitaxial films. Despite fatigue, endurance in epitaxial La-doped films is more than 1010 cycles, and this good property is accompanied by excellent retention of more than 10 years. These results demonstrate that wake-up effect and endurance-retention dilemma are not intrinsic in La-doped Hf0.5Zr0.5O2.
The metastable orthorhombic phase of hafnia is generally obtained in polycrystalline films, whereas in epitaxial films, its formation has been much less investigated. We have grown Hf0.5Zr0.5O2 films by pulsed laser deposition, and the growth window (temperature and oxygen pressure during deposition and film thickness) for epitaxial stabilization of the ferroelectric phase is mapped. The remnant ferroelectric polarization, up to around 24 uC/cm2, depends on the amount of orthorhombic phase and interplanar spacing and increases with temperature and pressure for a fixed film thickness. The leakage current decreases with an increase in thickness or temperature, or when decreasing oxygen pressure. The coercive electric field (EC) depends on thickness (t) according to the coercive electric field (Ec) - thickness (t)-2/3 scaling, which is observed for the first time in ferroelectric hafnia, and the scaling extends to thicknesses down to around 5 nm. The proven ability to tailor the functional properties of high-quality epitaxial ferroelectric Hf0.5Zr0.5O2 films paves the way toward understanding their ferroelectric properties and prototyping devices.
The effects of space charges on hysteresis loops and field distributions in ferroelectrics have been investigated numerically using the phenomenological Landau-Ginzburg-Devonshire theory. Cases with the ferroelectric fully and partially depleted have been considered. In general, increasing the number of charged impurities results in a lowering of the polarization and coercive field values. Squarer loops were observed in the partially depleted cases and a method was proposed to identify fully depleted samples experimentally from dielectric and polarization measurements alone. Unusual field distributions found for higher dopant concentrations have some interesting implications for leakage mechanisms and limit the range of validity of usual semiconductor equations for carrier transport.