Direct Observation of Structural Deformation Immunity for Understanding Oxygen Plasma Treatment-Enhanced Resistive Switching in HfOx-Based Memristive Devices.

Oxygen ions' migration is the fundamental resistive switching (RS) mechanism of the binary metal oxides-based memristive devices, and recent studies have found that the RS performance can be enhanced through appropriate oxygen plasma treatment (OPT). However, the lack of experimental evidence observed directly from the microscopic level of materials and applicable understanding of how OPT improves the RS properties will cause significant difficulties in its further application. In this work, we apply scanning probe microscope (SPM)-based techniques to study the OPT-enhanced RS performance in prototypical HfOx based memristive devices through in situ morphology and electrical measurements. It is first found that the structural deformations in HfOx nanofilm induced by migration of oxygen ions and interfacial electrochemical reactions can be recovered by OPT effectively. More importantly, such structural deformations no longer occur after OPT due to the strengthening in lattice structure, which directly illustrates the enhanced quantity of HfOx nanofilm and the nature of enhanced RS properties after OPT. Finally, the underlying mechanisms of OPT-enhanced RS performance are analyzed by the results of X-ray photoelectron spectroscopic (XPS) surface analysis. In the OPT-enhanced HfOx nanofilm, oxygen vacancies in crystalline regions can be remarkably reduced by active oxygen ions' implantation. The oxygen ions transport will depend considerably on the grain boundaries and OPT-enhanced lattice structure will further guarantee the stability of conductive filaments, both of which ensure the uniformity and repeatability in RS processes. This study could provide a scientific basis for improving RS performance of oxides-based memristive devices by utilizing OPT.

Effect of orientation on polarization switching and fatigue of Bi3.15Nd0.85Ti2.99Mn0.01O12 thin films at both low and elevated temperatures.

Bi3.15Nd0.85Ti2.99Mn0.01O12 (BNTM) thin films with (200)-orientations, (117)-orientations, and mixed-orientations were prepared by sol-gel methods. The influence of orientations on polarization fatigue behaviors of BNTM thin films were systematically investigated at both low and elevated temperatures. It was found that the changed trends of the polarization fatigue of (200)-oriented and (117)-oriented BNTM thin films at elevated temperatures were opposite. The fatigue properties become exacerbated for the (200)-oriented ones and become improved for the (117)-oriented ones, while the reduction of remanent polarization first decreases and then increases for the mixed-oriented ones. It can be assumed that the different roles played by domain walls and interface layer with increasing T in these thin films have caused such differences, which was certified by the lower activation energies (0.12-0.13 eV) of (200)-oriented BNTM thin films compared to those of BNTM thin films (0.17-0.31 eV) with other orientations through the temperature-dependent impedance spectra analysis. With the aid of piezoresponse force microscopy (PFM), the non-neutral tail-to-tail or head-to-head polarization configurations with greater probabilities for (117)-oriented and mixed-oriented thin films were found, while a majority of the neutral head-to-tail polarization configurations can be observed for (200)-oriented ones.

Two-dimensional polar metals in KNbO3/BaTiO3 superlattices: first-principle calculations.

Polar metals, commonly defined by the coexistence of polar structure and metallicity, are thought to be scarce because free carriers eliminate internal dipoles that may arise owing to asymmetric charge distributions. By using first-principle electronic structure calculations, we explored the possibility of producing metallic states in the polar/nonpolar KNbO3/BaTiO3 superlattice (SL) composed of two prototypical ferroelectric materials: BaTiO3 (BTO) and KNbO3 (KNO). Two types of polar/nonpolar interfaces, p-type (KO)-/(TiO2)0 and n-type (NbO2)+/(BaO)0, which can be constituted into two symmetric NbO2/BaO-NbO2/BaO (NN-type) and KO/TiO2-KO/TiO2 (PP-type) SL, as well as one asymmetric KO/TiO2-NbO2/BaO (PN-type) SL. The spatial distribution of ferroelectric distortions and their conductive properties are found to be extraordinarily sensitive to the interfacial configurations. An insulator-to-metal transition is found in each unit cell of the symmetric interfacial SL models: one exhibiting quasi-two-dimensional n-type conductivity for NN-type SL, while the other being quasi-two-dimensional p-type conductivity for PP-type SL. The anisotropic coexistence of in-plane orientation of free carriers and out-of-plane orientation of ferroelectric polarization in KNO/BTO SL indicates that in-plane free carriers can not eliminate the out-of-plane dipoles. Our results provide a road map to create two-dimensional polar metals in insulating perovskite oxide SL, which is expected to promote applications of new quantum devices.

Temperature-Dependent Domain Dynamics and Electrical Properties of Nd-doped Bi4Ti2.99Mn0.01O12 Thin Films in Fatigue Process.

Bi4Ti2.99Mn0.01O12 (BTM) thin films with different ratio of neodymium (Nd) doping were prepared on Pt(111)/Ti/SiO2/Si(100) substrates through a sol-gel method. The effects of Nd doping on domain dynamics and temperature-dependent fatigue behaviors of BTM thin films were systematically studied. The polarization fatigues of BTM (not doped) and Bi3.5Nd0.5Ti2.99Mn0.01O12 (BNTM05) thin films first get better with the increasing temperature (T) from 300 to 350 K and then become worse from 350 to 400 K, while Bi3.15Nd0.85Ti2.99Mn0.01O12 (BNTM85) thin films show enhanced fatigue endurance from 300 to 400 K. It can be shown that the long-range diffusion of oxygen vacancies in BTM thin film happens more easily through the impedance spectra analysis with T from 300 to 475 K, which can be verified by a lower activation energies (0.13⁻0.14 eV) compared to those of BNTM05 and BNTM85 (0.17⁻0.21 eV). Using a temperature-dependent piezoresponse force microscopy (PFM), we have found more responsive domain fragments in Nd-substituted films. The microscopic domain evolution from 298 to 448 K was done to further explain that the domain wall unpinning effect has been enhanced with increasing T. The correlation between microscopic domain dynamics and macroscopic electrical properties clearly demonstrates the effects of charged domain wall in Nd-doped BTM thin films during the fatigue tests.