Isotope Exchange Raman Spectroscopy (IERS): A Novel Technique to Probe Physicochemical Processes In Situ.

A novel in situ methodology for the direct study of mass-transport properties in oxides with spatial and unprecedented time resolution, based on Raman spectroscopy coupled to isothermal isotope exchanges, is developed. Changes in the isotope concentration, resulting in a Raman frequency shift, can be followed in real time, which is not accessible by conventional methods, enabling complementary insights for the study of ion-transport properties of electrode and electrolyte materials for advanced solid-state electrochemical devices. The proof of concept and strengths of isotope exchange Raman spectroscopy (IERS) is demonstrated by studying the oxygen isotope back-exchange in gadolinium-doped ceria (CGO) thin films. Resulting oxygen self-diffusion and surface exchange coefficients are compared to conventional time-of-flight secondary-ion mass spectrometry (ToF-SIMS) characterization and literature values, showing good agreement, while at the same time providing additional insight, challenging established assumptions. IERS captivates through its rapidity, simple setup, non-destructive nature, cost effectiveness, and versatile fields of application and thus can readily be integrated as new standard tool for in situ and operando characterization in many laboratories worldwide. The applicability of this method is expected to consolidate the understanding of elementary physicochemical processes and impact various emerging fields including solid oxide cells, battery research, and beyond.

Nanostructured La0.75Sr0.25Cr0.5Mn0.5O3-Ce0.8Sm0.2O2 Heterointerfaces as All-Ceramic Functional Layers for Solid Oxide Fuel Cell Applications.

The use of nanostructured interfaces and advanced functional materials opens up a new playground in the field of solid oxide fuel cells. In this work, we present two all-ceramic thin-film heterostructures based on samarium-doped ceria and lanthanum strontium chromite manganite as promising functional layers for electrode application. The films were fabricated by pulsed laser deposition as bilayers or self-assembled intermixed nanocomposites. The microstructural characterization confirmed the formation of dense, well-differentiated, phases and highlighted the presence of strong cation intermixing in the case of the nanocomposite. The electrochemical properties─solid/gas reactivity and in-plane conductivity─are strongly improved for both heterostructures with respect to the single-phase constituents under anodic conditions (up to fivefold decrease of area-specific resistance and 3 orders of magnitude increase of in-plane conductivity with respect to reference single-phase materials). A remarkable electrochemical activity was also observed for the nanocomposite under an oxidizing atmosphere, with no significant decrease in performance after 400 h of thermal aging. This work shows how the implementation of nanostructuring strategies not only can be used to tune the properties of functional films but also results in a synergistic enhancement of the electrochemical performance, surpassing the parent materials and opening the field for the fabrication of high-performance nanostructured functional layers for application in solid oxide fuel cells and symmetric systems.

Planar and Transparent Memristive Devices Based on Titanium Oxide Coated Silver Nanowire Networks with Tunable Switching Voltage.

Threshold switching devices are fundamental active elements in more than Moore approaches, integrating the new generation of non-volatile memory devices. Here, the authors report an in-plane threshold resistive switching device with an on/off ratio above 106 , a low resistance state of 10 to 100 kΩ and a high resistance state of 10 to 100 GΩ. Our devices are based on nanocomposites of silver nanowire networks and titanium oxide, where volatile unipolar threshold switching takes place across the gap left by partially spheroidized nanowires. Device reversibility depends on the titanium oxide thickness, while nanowire network density determines the threshold voltage, which can reach as low as 0.16 V. The switching mechanism is explained through percolation between metal-semiconductor islands, in a combined tunneling conduction mechanism, followed by a Schottky emission generated via Joule heating. The devices are prepared by low-cost, atmospheric pressure, and scalable techniques, enabling their application in printable, flexible, and transparent electronics.

Integration of LaMnO3+δ films on platinized silicon substrates for resistive switching applications by PI-MOCVD.

The next generation of electronic devices requires faster operation velocity, higher storage capacity and reduction of the power consumption. In this context, resistive switching memory chips emerge as promising candidates for developing new non-volatile memory modules. Manganites have received increasing interest as memristive material as they exhibit a remarkable switching response. Nevertheless, their integration in CMOS-compatible substrates, such as silicon wafers, requires further effort. Here the integration of LaMnO3+δ as memristive material in a metal-insulator-metal structure is presented using a silicon-based substrate and the pulsed injection metal organic chemical vapour deposition technique. We have developed three different growth strategies with which we are able to tune the oxygen content and Mn oxidation state moving from an orthorhombic to a rhombohedral structure for the active LaMnO3+δ material. Furthermore, a good resistive switching response has been obtained for LaMnO3+δ-based devices fabricated using optimized growth strategies.

Unveiling the Outstanding Oxygen Mass Transport Properties of Mn-Rich Perovskites in Grain Boundary-Dominated La0.8Sr0.2(Mn1-x Co x )0.85O3±Î´ Nanostructures.

Ion transport in solid-state devices is of great interest for current and future energy and information technologies. A superior enhancement of several orders of magnitude of the oxygen diffusivity has been recently reported for grain boundaries in lanthanum-strontium manganites. However, the significance and extent of this unique phenomenon are not yet established. Here, we fabricate a thin film continuous composition map of the La0.8Sr0.2(Mn1-x Co x )0.85O3±Î´ family revealing a substantial enhancement of the grain boundary oxygen mass transport properties for the entire range of compositions. Through isotope-exchange depth profiling coupled with secondary ion mass spectroscopy, we show that this excellent performance is not directly linked to the bulk of the material but to the intrinsic nature of the grain boundary. In particular, the great increase of the oxygen diffusion in Mn-rich compositions unveils an unprecedented catalytic performance in the field of mixed ionic-electronic conductors. These results present grain boundaries engineering as a novel strategy for designing highly performing materials for solid-state ionics-based devices.