Discovery of robust yet reversibly switchable electric dipoles at reduced dimensions is critical in advancing nanoelectronics devices. Energy bands flat in momentum space generate robust localized states that are activated independently of each other. We determined flat bands exist and induce robust yet independently switchable dipoles exhibiting a unique ferroelectricity in HfO2. Flat polar phonon bands in HfO2 cause extreme localization of electric dipoles within its irreducible half-unit-cell-widths (~3 Å). Contrary to conventional ferroelectrics with spread dipoles, those intrinsically localized dipoles are stable against extrinsic effects such as domain walls, surface exposure, and even down-to-angstrom-scale miniaturization. Moreover, the sub-nm-scale dipoles are individually switchable without creating any domain-wall energy cost. This offers unexpected opportunities for ultimately-dense unit-cell-by-unit-cell ferroelectric switching devices directly integrable into silicon technology.

Inorganic/organic nanocomposite counter electrodes comprised of sheetlike CoS nanoparticles dispersed in polystyrenesulfonate-doped poly(3,4-ethylenedioxythiophene (CoS/PEDOT:PSS) offer a synergistic effect on catalytic performance toward the reduction of triiodide for dye-sensitized solar cells (DSSCs), yielding 5.4% power conversion efficiency, which is comparable to that of the conventional platinum counter electrode (6.1%). The electrochemical impedance spectroscopy (EIS) and cyclic voltammetry measurements revealed that the composite counter electrodes exhibited better catalytic activity, fostering rate of triiodide reduction, than that of pristine PEDOT: PSS electrode. The simple preparation of composite (CoS/PEDOT:PSS) electrode at low temperature with improved electrocatalytic properties are feasible to apply in flexible substrates, which is at most urgency for developing novel counter electrodes for lightweight flexible solar cells.

The ferroelectricity in ultrathin HfO2 offers a viable alternative to ferroelectric memory. A reliable switching behavior is required for commercial applications; however, many intriguing features of this material have not been resolved. Herein, we report an increase in the remnant polarization after electric field cycling, known as the “wake-up” effect, in terms of the change in the polarization-switching dynamics of a Si-doped HfO2 thin film. Compared with a pristine specimen, the Si-doped HfO2 thin film exhibited a partial increase in polarization after a finite number of ferroelectric switching behaviors. The polarization-switching behavior was analyzed using the nucleation-limited switching model characterized by a Lorentzian distribution of logarithmic domain-switching times. The polarization switching was simulated using the Monte Carlo method with respect to the effect of defects. Comparing the experimental results with the simulations revealed that the wake-up effect in the HfO2 thin film is accompanied by the suppression of disorder.

No abstract

We report on the ferroelectricity of a Y-doped HfO2 thin film epitaxially grown on Si substrate, with an yttria-stabilized zirconia buffer layer pre-deposited on the substrate. Piezoresponse force microscopy results show the ferroelectric domain pattern, implying the existence of ferroelectricity in the epitaxial HfO2 film. The epitaxially stabilized HfO2 film in the form of a metal-ferroelectric-insulator-semiconductor structure exhibits ferroelectric hysteresis with a clear ferroelectric switching current in polarization-voltage measurements. The HfO2 thin film also demonstrates ferroelectric retention comparable to that of current perovskite-based metal-ferroelectric-insulator-semiconductor structures.

Oxygen-vacancy-ordered brownmillerite oxides offer a reversible topotactic phase transition by significantly varying the oxygen stoichiometry of the material without losing its lattice framework. This phase transition leads to substantial changes in the physical and chemical properties of brownmillerite oxides, including electrical and ion conductivity, magnetic state, and oxygen diffusivity. In this study, the variations in the resistive switching mode of the epitaxial brownmillerite SrFeO 2.5 thin film in the device were studied by systematically controlling the oxygen concentration, which could be varied by changing the compliance current during the first electroforming step. Depending on the compliance current, the SrFeO 2.5 devices exhibited either low-power bipolar resistive switching or complementary resistive switching behaviors. A physical model based on the internal redistribution of oxygen ions between the interfaces with the top and the bottom electrodes was developed to explain the complementary resistive switching behavior. This model was experimentally validated using impedance spectroscopy. Finally, the gradual conductance variation in the brownmillerite SrFeO 2.5 thin films was exploited to realize synaptic learning.

The recent demand for analogue devices for neuromorphic applications requires modulation of multiple nonvolatile states. Ferroelectricity with multiple polarization states enables neuromorphic applications with various architectures. However, deterministic control of ferroelectric polarization states with conventional ferroelectric materials has been met with accessibility issues. Here, we report unprecedented stable accessibility with robust stability of multiple polarization states in ferroelectric HfO 2 . Through the combination of conventional voltage measurements, hysteresis temperature dependence analysis, piezoelectric force microscopy, first-principles calculations, and Monte Carlo simulations, we suggest that the unprecedented stability of intermediate states in ferroelectric HfO 2 is due to the small critical volume size for nucleation and the large activation energy for ferroelectric dipole flipping. This work demonstrates the potential of ferroelectric HfO 2 for analogue device applications enabling neuromorphic computing.

No abstract