arXiv subjects

Alex Morata

Publications and source records attributed to Alex Morata.

14 recordsLinked to original sources

arXiv2026

Structure-driven analog optical control in ion-pumped SrFeO$_{3-\delta}$ thin-film devices

Electrochromic devices (ECDs) offer a compelling route toward low-power, non-emissive optical modulators with nonvolatile states. However, their widespread implementation is hindered by limitations in operating voltage, switching speed, color tunability, and long-term stability. Mixed ionic-electronic conductors (MIECs) provide a promising alternative platform, enabling optical modulation through ion-driven redox and structural transformations. Oxygen-based MIECs offer enhanced durability, environmental robustness, and compatibility with oxide electronics and silicon photonics, yet remain largely underexplored for electrochromic and photonic applications. Here, we demonstrate structure-driven analog optical control in an ion-pumped SrFeO$_{3-\delta}$ thin-film device by undergoing reversible oxygen-driven phase transitions between brownmillerite and perovskite structures. Phase transition is accompanied by pronounced changes in its electronic structure and optical constants. By harnessing these ion-induced structural transformations and integrating an optically passive Al$_2$O$_3$ interference layer, we achieve continuous and reversible modulation of optical transmittance and color. These results provide a general framework for ion-driven analog photonic and electrochromic devices and highlight the potential of oxygen-based MIECs for next-generation ionochromic systems compatible with silicon-based photonic platforms.

physics.app-ph↗

arXiv2026

Wide-Surface Furnace for In Situ X-Ray Diffraction of Combinatorial Samples using a High-Throughput Approach

The combinatorial approach applied to functional oxides has enabled the production of material libraries that formally contain infinite compositions. A complete ternary diagram can be obtained by pulsed laser deposition (PLD) on 100 mm silicon wafers. However, interest in such materials libraries is only meaningful if high-throughput characterization enables the information extraction from the as-deposited library in a reasonable time. While much commercial equipment allows for XY-resolved characterization at room temperature, very few sample holders have been made available to investigate structural, chemical, and functional properties at high temperatures in controlled atmospheres. In the present work, we present a furnace that enables the study of 100 mm wafers as a function of temperature. This furnace has a dome to control the atmosphere, typically varying from nitrogen gas to pure oxygen atmosphere with external control. We present the design of such a furnace and an example of X-ray diffraction (XRD) and fluorescence (XRF) measurements performed at the DiffAbs beamline of the SOLEIL synchrotron. We apply this high-throughput approach to a combinatorial library up to 735 {\textdegree}C in nitrogen and calculate the thermal expansion coefficients (TEC) of the ternary system using custom-made MATLAB codes. The TEC analysis revealed the potential limitations of Vegard's law in predicting lattice variations for high-entropy materials.

cond-mat.mtrl-sci↗

arXiv2024

Analog control of electrical conductivity in La0.5Sr0.5FeO3-{\delta} through oxygen deficiency induced magnetic transition

Switchability of materials properties by applying controlled stimuli such as voltage pulses is an emerging field of study with applicability in adaptive and programmable devices like neuromorphic transistors or non-emissive smart displays. One of the most exciting approaches to modulate materials performance is mobile ion/vacancy insertion for inducing changes in relevant electrical, optical, or magnetic properties, among others. Unveiling the interplay between changes in the concentration of mobile defects (like oxygen vacancies) and functional properties in relevant materials represents a step forward for underpinning the emerging oxide iontronics discipline. In this work, electrochemical oxide-ion pumping cells were fabricated for an analog control of the oxygen stoichiometry in thin films of mixed ionic-electronic conductor La0.5Sr0.5FeO3-{\delta}. We demonstrate over more than 4 orders of magnitude electronic conductivity control within the same crystallographic phase through the precise and continuous voltage control of the oxygen stoichiometry. We show that behind the modification of the transport properties of the material lays a paramagnetic-to-antiferromagnetic transition. We exploit such magnetoelectric coupling to show control over the exchange interaction between La0.5Sr0.5FeO3-{\delta} and a ferromagnetic Co layer deposited on top.

cond-mat.mtrl-sci↗

arXiv2024

Solid-State Oxide-Ion Synaptic Transistor for Neuromorphic Computing

Neuromorphic hardware facilitates rapid and energy-efficient training and operation of neural network models for artificial intelligence. However, existing analog in-memory computing devices, like memristors, continue to face significant challenges that impede their commercialization. These challenges include high variability due to their stochastic nature. Microfabricated electrochemical synapses offer a promising approach by functioning as an analog programmable resistor based on deterministic ion-insertion mechanisms. Here, we developed an all-solid-state oxide-ion synaptic transistor employing $\text{Bi}_2\text{V}_{0.9}\text{Cu}_{0.1}\text{O}_{5.35}$ as a superior oxide-ion conductor electrolyte and $\text{La}_\text{0.5}\text{Sr}_\text{0.5}\text{F}\text{O}_\text{3-$\delta$}$ as a variable resistance channel able to efficiently operate at temperatures compatible with conventional electronics. Our transistor exhibits essential synaptic behaviors such as long- and short-term potentiation, paired-pulse facilitation, and post-tetanic potentiation, mimicking fundamental properties of biological neural networks. Key criteria for efficient neuromorphic computing are satisfied, including excellent linear and symmetric synaptic plasticity, low energy consumption per programming pulse, and high endurance with minimal cycle-to-cycle variation. Integrated into an artificial neural network (ANN) simulation for handwritten digit recognition, the presented synaptic transistor achieved a 96% accuracy on the MNIST dataset, illustrating the effective implementation of our device in ANNs. These findings demonstrate the potential of oxide-ion based synaptic transistors for effective implementation in analog neuromorphic computing based on iontronics.

cs.ET↗

arXiv2024

Optoionic Impedance Spectroscopy (OIS): a model-less technique for in-situ electrochemical characterization of mixed ionic electronic conductors

Functional properties of mixed ionic electronic conductors (MIECs) can be radically modified by (de)insertion of mobile charged defects. A complete control of this dynamic behaviour has multiple applications in a myriad of fields including advanced computing, data processing, sensing or energy conversion. However, the effect of different MIECs state-of-charge is not fully understood yet and there is a lack of strategies for fully controlling the defect content in a material. In this work we present a model-less technique to characterize ionic defect concentration and ionic insertion kinetics in MIEC materials: Optoionic Impedance Spectroscopy (OIS). The proof of concept and advantages of OIS are demonstrated by studying the oxygen (de)insertion in thin films of hole-doped perovskite oxides. Ion migration into/out of the studied materials is achieved by the application of an electrochemical potential, achieving stable and reversible modification of its optical properties. By tracking the dynamic variation of optical properties depending on the gating conditions, OIS enables to extract electrochemical parameters involved in the electrochromic process. The results demonstrate the capability of the technique to effectively characterize the kinetics of single- and even multi- layer systems. The technique can be employed for studying underlying mechanisms of the response characteristics of MIEC-based devices.

physics.app-ph↗

arXiv2023

Insights into the LiMn2O4 Cathode Stability in Aqueous Electrolyte

LiMn2O4 (LMO), cathodes present large stability when cycled in aqueous electrolytes, contrasting its behavior in conventional organic electrolytes in Lithium-ion batteries (LIBs). To elucidate the mechanisms underlying this distinctive behavior, we employ unconventional characterization techniques, including Variable Energy Positron Annihilation Lifetime Spectroscopy (VEPALS), Tip-Enhanced Raman Spectroscopy (TERS) and macro-Raman Spectroscopy (with mm-size laser spot). These still rather unexplored techniques in the battery field provide complementary information across different length scales, revealing previously hidden features. VEPALS offers atomic-scale insights, uncovering cationic defects and sub-nanometer pores that tend to collapse with cycling. TERS, operating at the nanometric range at the surface, captured the presence of Mn3O4 and its dissolution with cycling, elucidating dynamic changes during operation. Additionally, TERS highlights SO42- accumulation at grain boundaries. Macro-Raman Spectroscopy focuses on the micrometer scale, depicting small changes in the cathode's long-range order, suggesting a slow but progressive loss of crystalline quality under operation. Integrating these techniques provides a comprehensive assessment of LMO cathode stability in aqueous electrolytes, offering multifaceted insights into phase and defect evolution that can help to rationalize the origin of such stability when compared to conventional organic electrolytes. Our findings advance the understanding of LMO behavior in aqueous environments and provide guidelines for its development for next-generation LIBs.

cond-mat.mtrl-sci↗

arXiv2023

Ion Intercalation in Lanthanum Strontium Ferrite for Aqueous Electrochemical Energy Storage Devices

Ion intercalation of perovskite oxides in liquid electrolytes is a very promising method for controlling their functional properties while storing charge, which opens the potential application in different energy and information technologies. Although the role of defect chemistry in the oxygen intercalation in a gaseous environment is well established, the mechanism of ion intercalation in liquid electrolytes at room temperature is poorly understood. In this study, the defect chemistry during ion intercalation of La0.5Sr0.5FeO3-{\delta} thin films in alkaline electrolytes is studied. Oxygen and proton intercalation into the LSF perovskite structure is observed at moderate electrochemical potentials (0.5 V to -0.4 V), giving rise to a change in the oxidation state of Fe (as a charge compensation mechanism). The variation of the concentration of holes as a function of the intercalation potential was characterized by in-situ ellipsometry and the concentration of electron holes was indirectly quantified for different electrochemical potentials. Finally, a dilute defect chemistry model that describes the variation of defect species during ionic intercalation was developed.

cond-mat.mtrl-sci↗

arXiv2022

Ultrafast crystallization and sintering of Li1.5Al0.5Ge1.5(PO4)3 glass and its impact on ion conduction

Li1.5Al0.5Ge1.5(PO4)3 (LAGP) is among the most promising solid electrolytes for the next generation all-solid-state lithium batteries. However, preparing LAGP electrolytes is timeand energy-intensive. In this work, LAGP glassy powders were sintered and crystallized in 180 seconds by ultrafast high-temperature sintering (UHS) under conditions attractive for continuous industrial processes (i.e., ambient pressure and atmosphere). The fast heating rates characteristic of UHS significantly delay crystallization, potentially decoupling crystallization and sintering. Furthermore, EIS characterizations reveal that LAGP sintered and crystallized by UHS has an ionic conductivity of 1.15 10-4 S/cm, slightly lower than conventionally annealed samples (1.75 10-4 S/cm). The lower conductivity can be attributed to poorer intergrain contact. To overcome this issue, additives such as B2O3 and Li3BO3 are used, resulting in 2 and 5 times higher grain boundary conductivity for LAGP+1 wt B2O3 and LAGP+1 wt Li3BO3, respectively, compared to LAGP. Overall, this work provides insights into unraveling the impact of UHS sintering on the LAGP Li+ conduction mechanism.

cond-mat.mtrl-sci↗

arXiv2022

Functional thin films as cathode/electrolyte interlayers: a strategy to enhance the performance and durability of solid oxide fuel cells

Electrochemical devices such as solid oxide fuel cells (SOFC) may greatly benefit from the implementation of nanoengineered thin-film multifunctional layers providing, alongside enhanced electrochemical activity, improved mechanical, and long-term stability. In this study, an ultrathin (400 nm) bilayer of samarium-doped ceria and a self-assembled nanocomposite made of Sm0.2Ce0.8O1.9-La0.8Sr0.2MnO3-$\delta$ was fabricated by pulsed laser deposition and is employed as a functional oxygen electrode in an anode-supported solid oxide fuel cell. Introducing the functional bilayer in the cell architecture results in a simple processing technique for the fabrication of high-performance fuel cells (power density 1.0 W.cm-2 at 0.7 V and 750 $^\circ$C). Durability tests were carried out for up to 1500 h, showing a small degradation under extreme operating conditions of 1 A.cm-2, while a stable behaviour at 0.5 A.cm-2. Post-test analyses, including scanning and transmission electron microscopy and electrochemical impedance spectroscopy, demonstrate that the nanoengineered thin film layers remain mostly morphologically stable after the operation.

cond-mat.mtrl-sci↗

arXiv2021

Pushing the Study of Point Defects in Thin Film Ferrites to Low Temperatures Using In Situ Ellipsometry

Unveiling point defects concentration in transition metal oxide thin films is essential to understand and eventually control their functional properties, employed in an increasing number of applications and devices. Despite this unquestionable interest, there is a lack of available experimental techniques able to estimate the defect chemistry and equilibrium constants in such oxides at intermediate-to-low temperatures. In this study, the defect chemistry of a relevant material such as La1-xSrxFeO3-d (LSF) with (x = 0.2, 0.4 and 0.5 (LSF20, LSF40 and LSF50 respectively) is obtained by using a novel in situ spectroscopic ellipsometry approach applied to thin films. Through this technique, the concentration of holes in LSF is correlated to measured optical properties and its evolution with temperature and oxygen partial pressure is determined. In this way, a systematic description of defect chemistry in LSF thin films in the temperature range from 350dC to 500dC is obtained for the first time, which represents a step forward in the understanding of LSF20, LSF40 and LSF50 for emerging low temperature applications.

cond-mat.mtrl-sci↗

arXiv2019

Unraveling Bulk and Grain Boundary Electrical Properties in La0.8Sr0.2Mn1-yO3 Thin Films

Grain boundaries in Sr-doped LaMnO3 thin films have been shown to strongly influence the electronic and oxygen mass transport properties, being able to profoundly modify the nature of the material. The unique behaviour of the grain boundaries can be correlated with substantial modifications of the cation concentration at the interfaces, which can be tuned by changing the overall cationic ratio in the films. In this work, we study the electronic properties of La0.8Sr0.2Mn1-yO3 thin films with variable Mn content. The influence of the cationic composition on the grain boundary and grain bulk electronic properties is elucidated by studying the manganese valence state evolution using spectroscopy techniques and by confronting the electronic properties of epitaxial and polycrystalline films. Substantial differences in the electronic conduction mechanism are found in the presence of grain boundaries and depending on the manganese content. Moreover, the unique defect chemistry of the nanomaterial is elucidated by measuring the electrical resistance of the thin films as a function of oxygen partial pressure, disclosing the importance of the cationic local non-stoichiometry on the thin films behavior.

cond-mat.mtrl-sci↗

arXiv2018

Engineering mass transport properties in oxide ionic and mixed ionic electronic thin film ceramic conductors for energy applications

New emerging disciplines such as Nanoionics and Iontronics are dealing with the exploitation of mesoscopic size effects in materials, which become visible (if not predominant) when downsizing the system to the nanoscale. Driven by the worldwide standardisation of thin film deposition techniques, the access to radically different properties than those found in the bulk macroscopic systems can be accomplished. This opens up promising approaches for the development of advanced microdevices, by taking advantage of the nanostructural deviations found in nanometre sized, interface dominated materials compared to the ideal relaxed structure of the bulk. A completely new set of functionalities can be explored, with implications in many different fields such as energy conversion and storage, or information technologies. This manuscript reviews the strategies, employed and foreseen, for engineering mass transport properties in thin film ceramics, with the focus in oxide ionic and mixed ionic electronic conductors and their application in micro power sources.

cond-mat.mtrl-sci↗

arXiv2018

Insights into the enhancement of oxygen mass transport properties of strontium doped lanthanum manganite interface-dominated thin films

Strontium doped lanthanum manganite thin films were deposited by pulsed laser deposition on yttria stabilized zirconia single crystals for a comprehensive electrochemical characterization of the material acting as a cathode. A physically meaningful electrical model was employed to fit the electrochemical impedance spectroscopy results in order to extract the main oxygen mass transport parameters as a function of the temperature and oxygen partial pressure. The oxygen diffusion and surface exchange coefficients extracted from the analysis showed several orders of magnitude of enhancement with respect to the bulk values reported in the literature and an unexpectedly low dependence with the oxygen partial pressure. Different observations were combined to propose a mechanism for the enhanced incorporation of oxygen in interface dominated thin films mainly based on the high concentration of oxygen vacancies expected in the grain boundaries.

cond-mat.mtrl-sci↗

arXiv2018

Unveiling the outstanding oxygen mass transport properties of Mn-rich perovskites in grain boundary-dominated La0.8Sr0.2(Mn1-xCox)0.85O3-d 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 is not yet established. Here, we fabricate a thin film continuous composition map of the La0.8Sr0.2(Mn1-xCox)0.85O3-d 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 to 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.

cond-mat.mtrl-sci↗