Designing Strained Interface Heterostructures for Memristive Devices.

Ionic heterostructures are used as a strain-modulated memristive device based on the model system Gd0.1 Ce0.9 O2-δ /Er2 O3 to set and tune the property of "memristance." The modulation of interfacial strain and the interface count is used to engineer the Roff /Ron ratio and the persistence of the system. A model describing the variation of mixed ionic-electronic mobilities and defect concentrations is presented.

Role of Associated Defects in Oxygen Ion Conduction and Surface Exchange Reaction for Epitaxial Samaria-Doped Ceria Thin Films as Catalytic Coatings.

Samaria-doped ceria (SDC) thin films are particularly important for energy and electronic applications such as microsolid oxide fuel cells, electrolyzers, sensors, and memristors. In this paper, we report a comparative study investigating ionic conductivity and surface reactions for well-grown epitaxial SDC films varying the samaria doping concentration. With increasing doping above 20 mol % of samaria, an enhancement in the defect association is observed by Raman spectroscopy. The role of such associated defects on the films̀ oxygen ion transport and exchange is investigated by electrochemical impedance spectroscopy and electrochemical strain microscopy (ESM). The measurements reveal that the ionic transport has a sharp maximum in ionic conductivity and drops in its activation energy down to 0.6 eV for 20 mol % doping. Increasing the doping concentration further up to 40 mol %, it raises the activation energy substantially by a factor of 2. We ascribe the sluggish transport kinetics to the "bulk" ionic-near ordering in case of the heavily doped epitaxial films. Analysis of the ESM first-order reversal curve measurements indicates that these associated defects may have a beneficial role by lowering the activation of the oxygen exchange "surface" reaction for heavily doped 40 mol % of samaria. In a model experiment, through a solid solution series of samaria doped ceria epitaxial films, we reveal that the occurrence of associated defects in the bulk affects the surface charging state of the SDC films to increase the exchange rates. The implication of these findings is the design of coatings with tuned oxygen surface exchange by controlling the bulk associated clusters for future electrocatalytic applications.

The effect of mechanical twisting on oxygen ionic transport in solid-state energy conversion membranes.

Understanding 'electro-chemo-mechanics' in oxygen ion conducting membranes represents a foundational step towards new energy devices such as micro fuel cells and oxygen or fuel separation membranes. For ionic transport in macro crystalline electrolytes, doping is conventionally used to affect oxygen ionic association/migration energies. Recently, tuning ionic transport in films through lattice strain conveyed by substrates or heterostructures has generated much interest. However, reliable manipulation of strain states to twist the ionic conduction in real micro energy devices remains intractable. Here, we demonstrate that the oxygen ionic conductivity clearly correlates with the compressive strain energy acting on the near order of the electrolyte lattices by comparing thin-film ceria-based membrane devices against substrate-supported flat structures. It is possible to capitalize on this phenomenon with a smart choice of strain patterns achieved through microelectrode design. We highlight the importance of electro-chemo-mechanics in the electrolyte material for the next generation of solid-state energy conversion microdevices.

A microdot multilayer oxide device: let us tune the strain-ionic transport interaction.

In this paper, we present a strategy to use interfacial strain in multilayer heterostructures to tune their resistive response and ionic transport as active component in an oxide-based multilayer microdot device on chip. For this, fabrication of strained multilayer microdot devices with sideways attached electrodes is reported with the material system Gd0.1Ce0.9O(2-δ)/Er2O3. The fast ionic conducting Gd0.1Ce0.9O(2-δ) single layers are altered in lattice strain by the electrically insulating erbia phases of a microdot. The strain activated volume of the Gd0.1Ce0.9O(2-δ) is investigated by changing the number of individual layers from 1 to 60 while keeping the microdot at a constant thickness; i.e., the proportion of strained volume was systematically varied. Electrical measurements showed that the activation energy of the devices could be altered by Δ0.31 eV by changing the compressive strain of a microdot ceria-based phase by more than 1.16%. The electrical conductivity data is analyzed and interpreted with a strain volume model and defect thermodynamics. Additionally, an equivalent circuit model is presented for sideways contacted multilayer microdots. We give a proof-of-concept for microdot contacting to capture real strain-ionic transport effects and reveal that for classic top-electrode contacting the effect is nil, highlighting the need for sideways electric contacting on a nanoscopic scale. The near order ionic transport interaction is supported by Raman spectroscopy measurements. These were conducted and analyzed together with fully relaxed single thin film samples. Strain states are described relative to the strain activated volumes of Gd0.1Ce0.9O(2-δ) in the microdot multilayer. These findings reveal that strain engineering in microfabricated devices allows altering the ionic conduction over a wide range beyond classic doping strategies for single films. The reported fabrication route and concept of strained multilayer microdots is a promising path for applying strained multilayer oxides as active new building blocks relevant for a broad range of microelectrochemical devices, e.g., resistive switching memory prototypes, resistive or electrochemical sensors, or as active catalytic solid state surface components for microfuel cells or all-solid-state batteries.