Hongchu Du

Spectromicroscopic insights for rational design of redox-based memristive devices.

The demand for highly scalable, low-power devices for data storage and logic operations is strongly stimulating research into resistive switching as a novel concept for future non-volatile memory devices. To meet technological requirements, it is imperative to have a set of material design rules based on fundamental material physics, but deriving such rules is proving challenging. Here, we elucidate both switching mechanism and failure mechanism in the valence-change model material SrTiO3, and on this basis we derive a design rule for failure-resistant devices. Spectromicroscopy reveals that the resistance change during device operation and failure is indeed caused by nanoscale oxygen migration resulting in localized valence changes between Ti4+ and Ti3+. While fast reoxidation typically results in retention failure in SrTiO3, local phase separation within the switching filament stabilizes the retention. Mimicking this phase separation by intentionally introducing retention-stabilization layers with slow oxygen transport improves retention times considerably.

Determination of the electrostatic potential distribution in Pt/Fe:SrTiO3/Nb:SrTiO3 thin-film structures by electron holography

We determined the electrostatic potential distribution in pristine Pt/Fe:SrTiO3/Nb:SrTiO3 structures by electron holography experiments, revealing the existence of a depletion layer extending into the Nb-doped bottom electrode. Simulations of potential profiles in metal-insulator-metal structures were conducted assuming different types and distributions of dopants. It is found that the presence of acceptor-type dopant concentrations at the Fe:SrTiO3/Nb:SrTiO3 interface with a donor-doped insulating layer provides a good match to the measured profile. Such acceptor-type interface concentrations may be associated with Sr vacancies on the Nb:SrTiO3 side of the bottom interface.

Oxygen Exchange Processes between Oxide Memristive Devices and Water Molecules

Resistive switching based on transition metal oxide memristive devices is suspected to be caused by the electric-field-driven motion and internal redistribution of oxygen vacancies. Deriving the detailed mechanistic picture of the switching process is complicated, however, by the frequently observed influence of the surrounding atmosphere. Specifically, the presence or absence of water vapor in the atmosphere has a strong impact on the switching properties, but the redox reactions between water and the active layer have yet to be clarified. To investigate the role of oxygen and water species during resistive switching in greater detail, isotope labeling experiments in a N2 /H218 O tracer gas atmosphere combined with time-of-flight secondary-ion mass spectrometry are used. It is explicitly demonstrated that during the RESET operation in resistive switching SrTiO3 -based memristive devices, oxygen is incorporated directly from water molecules or oxygen molecules into the active layer. In humid atmospheres, the reaction pathway via water molecules predominates. These findings clearly resolve the role of humidity as both oxidizing agent and source of protonic defects during the RESET operation.

Formation mechanism of Ruddlesden-Popper-type antiphase boundaries during the kinetically limited growth of Sr rich SrTiO3 thin films

We elucidated the formation process for Ruddlesden-Popper-type defects during pulsed laser deposition of Sr rich SrTiO3 thin films by a combined analysis of in-situ atomic force microscopy, low energy electron diffraction and high resolution scanning transmission electron microscopy. At the early growth stage of 1.5 unit cells, the excess Sr results in the formation of SrO on the surface, resulting in a local termination change from TiO2 to SrO, thereby forming a Sr rich (2 × 2) surface reconstruction. With progressive SrTiO3 growth, islands with thermodynamically stable SrO rock-salt structure are formed, coexisting with TiO2 terminated islands. During the overgrowth of these thermodynamically stable islands, both lateral as well as vertical Ruddlesden-Popper-type anti-phase boundaries are formed, accommodating the Sr excess of the SrTiO3 film. We suggest the formation of thermodynamically stable SrO rock-salt structures as origin for the formation of Ruddlesden-Popper-type antiphase boundaries, which are as a result of kinetic limitations confined to certain regions on the surface.

Controlled Charging of Ferroelastic Domain Walls in Oxide Ferroelectrics

Conductive domain walls (DWs) in ferroic oxides as device elements are a highly attractive research topic because of their robust and agile response to electric field. Charged DWs possessing metallic-type conductivity hold the highest promises in this aspect. However, their intricate creation, low stability, and interference with nonconductive DWs hinder their investigation and the progress toward future applications. Here, we find that conversion of the nominally neutral ferroelastic 90° DWs into partially charged DWs in Pb(Zr0.1Ti0.9)O3 thin films enables easy and robust control over the DW conductivity. By employing transmission electron microscopy, conductive atomic force microscopy and phase-field simulation, our study reveals that charging of the ferroelastic DWs is controlled by mutually coupled DW bending, type of doping, polarization orientation and work-function of the adjacent electrodes. Particularly, the doping outweighs other parameters in controlling the DW conductivity. Understanding the interplay of these key parameters not only allows us to control and optimize conductivity of such ferroelastic DWs in the oxide ferroelectrics but also paves the way for utilization of DW-based nanoelectronic devices in the future.

Electrically controlled transformation of memristive titanates into mesoporous titanium oxides via incongruent sublimation

Perovskites such as SrTiO3, BaTiO3, and CaTiO3 have become key materials for future energy-efficient memristive data storage and logic applications due to their ability to switch their resistance reversibly upon application of an external voltage. This resistance switching effect is based on the evolution of nanoscale conducting filaments with different stoichiometry and structure than the original oxide. In order to design and optimize memristive devices, a fundamental understanding of the interaction between electrochemical stress, stoichiometry changes and phase transformations is needed. Here, we follow the approach of investigating these effects in a macroscopic model system. We show that by applying a DC voltage under reducing conditions on a perovskite slab it is possible to induce stoichiometry polarization allowing for a controlled decomposition related to incongruent sublimation of the alkaline earth metal starting in the surface region. This way, self-formed mesoporous layers can be generated which are fully depleted by Sr (or Ba, Ca) but consist of titanium oxides including TiO and Ti3O with tens of micrometre thickness. This illustrates that phase transformations can be induced easily by electrochemical driving forces.

Au Nanoparticles as Template for Defect Formation in Memristive SrTiO3 Thin Films

We investigated the possibility of tuning the local switching properties of memristive crystalline SrTiO3 thin films by inserting nanoscale defect nucleation centers. For that purpose, we employed chemically-synthesized Au nanoparticles deposited on 0.5 wt%-Nb-doped SrTiO3 single crystal substrates as a defect formation template for the subsequent growth of SrTiO3. We studied in detail the resulting microstructure and the local conducting and switching properties of the SrTiO3 thin films. We revealed that the Au nanoparticles floated to the SrTiO3 surface during growth, leaving behind a distorted thin film region in their vicinity. By employing conductive-tip atomic force microscopy, these distorted SrTiO3 regions are identified as sites of preferential resistive switching. These findings can be attributed to the enhanced oxygen exchange reaction at the surface in these defective regions.