arXiv subjects

José Santiso

Publications and source records attributed to José Santiso.

12 recordsLinked to original sources

arXiv2026

Depth-Resolved Evolution of Buried Polar Topologies in a PbTiO3/SrTiO3 Superlattice

Polar topologies in complex oxides gives rise to a rich spectrum of emergent functionalities and are fundamentally governed by three-dimensional (3D) atomic structures. However, direct experimental determination of buried 3D polar configurations remains a longstanding challenge because conventional (scanning) transmission electron microscopy ((S)TEM) provides primarily projected structural information with limited depth sensitivity. Here, we combine depth-sectioning low-angle annular dark-field (LAADF) STEM, high-angle ADF (HAADF) STEM, and multislice electron ptychography (MEP) to directly visualize the depth-dependent atomic structure and polarization topology in a PTO/STO superlattice. Depth-sectioning STEM reveals pronounced focal-depth-dependent contrast variations and apparent splitting of Pb atomic columns, indicating significant structural heterogeneity along the beam direction. MEP reconstruction simultaneously resolves the Pb, Ti, and O sublattices with nanometer-scale depth resolution, enabling quantitative mapping of atomic displacements throughout the reconstructed volume. The resulting 3D atomic model reveals substantial depth-dependent displacements of Pb, Ti, and O atoms and a corresponding evolution of the polarization topology. Vortex-like polarization structures are observed near the specimen surfaces but become strongly suppressed within the interior, where distinct polarization configurations emerge. These findings show that polarization patterns observed in conventional projection images can arise from the superposition of multiple depth-dependent polar states and may obscure the underlying 3D polarization texture. Our findings establish a direct experimental link between local atomic displacements and depth-dependent polarization topology, opening new opportunities for investigating and engineering buried functional states in complex oxide nanostructures.

cond-mat.mtrl-sci↗

arXiv2026

Complex polar superstructure controlled thermal conductivity in ferroelectric PbTiO3/SrTiO3 superlattices

Integrating epitaxial thin films of ferroelectric PbTiO3 and paraelectric SrTiO3 into artificially layered periodic superlattices provides a unique platform for tuning strain, depolarization, and interfacial/surface energies, thereby accessing a rich phase diagram of topological polar structures (skyrmions, vortices, merons, or sinusoidal waves) and superstructures (polar supercrystals). Here we show that the 3D arrangement of polar vortices in a supercrystal suppresses thermal conductivity (k) of PTO/STO superlattices (SLs). The temperature dependence of k reflects the evolution of the polar superstructure, as determined by X-ray diffraction and transmission electron microscopy. The comparison with other SLs suggests that the 3D arrangement is crucial for controlling thermal conductivity beyond the usual interfacial scattering. Moreover, we observed an unexpected reduction in thermal conductivity with increasing superlattice thickness, a phenomenon reminiscent of phonon-wave Anderson localization. Our results show that complex polar superstructures can be useful active elements for modulating heat transport in technologies where control over heat dissipation is critical.

cond-mat.mtrl-sci↗

arXiv2026

Device-area selection of memristive transport regimes in epitaxial $Hf_{0.5}Zr_{0.5}O_{2}$-based ferroelectric devices

Ferroelectric memristive devices based on hafnia are promising systems for neuromorphic electronics, yet the interplay between polarization-modulated resistive changes and defect-mediated transport often leads to complex and debated switching mechanisms. Here, we investigate this competition in epitaxial Hf$_{0.5}$Zr$_{0.5}$O$_2$/La$_{0.67}$Sr$_{0.33}$MnO$_3$ heterostructures with Pt top electrodes by combining structural, ferroelectric, and memristive characterization with a statistical analysis across a broad range of device areas spanning three orders of magnitude. We identify two distinct memristive regimes with opposite resistance--voltage chiralities. Small devices exhibit a low-resistance state that scales inversely with area, consistent with area-distributed tunneling transport, while larger devices display an area-independent resistance indicative of localized conductive channels. A statistical nucleation model quantitatively captures this behavior and yields a crossover characteristic area $A^* \approx 10^3~μ\mathrm{m}^2$. This crossover also correlates with the onset of ferroelectric wake-up in larger devices, linking conductive-channel nucleation and oxygen-vacancy redistribution within a unified physical picture. These results establish lateral device size as a key parameter controlling the dominant transport mechanism in epitaxial hafnia-based devices.

cond-mat.mtrl-sci↗

arXiv2026

Thermodynamics of the ultrafast phase transition of vanadium dioxide

Ultrafast photoexcitation is an emerging route to selective control of phase transitions. However, it is difficult to determine which modes govern the transformation and how effectively they are targeted by photoexcitation. This is exemplified in vanadium dioxide, which transitions from a monoclinic insulator to a rutile metal upon heating or photoexcitation. There is a long-standing debate about whether this transition is electronically or structurally driven and whether the structural component is coherent, driven by a single structural mode or thermal in nature. In this work, we develop a simple thermodynamic framework based on temperature-dependent ultrafast pump-probe measurements and contrast it to microscopic-detail-free modelling to identify the driving mechanism of the transition, revealing that population of the full thermal phonon spectrum, especially high-frequency oxygen modes, is necessary to stabilize the metallic phase. Our approach can straightforwardly be applied to determine the nature of other photoinduced phase transitions without the need for complex multi-messenger experiments and can guide new control strategies, even for incoherent transitions.

cond-mat.str-el↗

arXiv2025

Beware of the water: Hidden hydrogenation of perovskite membranes made by the water-soluble sacrificial layer method

The fabrication of perovskite oxide free-standing films (membranes) by lift-off methods using water-soluble sacrificial layers is appealing because of the new mechanical degrees of freedom that these membranes present over conventional epitaxial films. However, little is known about how their fabrication process, and in particular the exposure to water during the etching step, affects their properties. Here, we investigate how membranes of two perovskite archetypes, antiferroelectric PbZrO3 and paraelectric SrTiO3, are affected by water-based etching step. Using Raman spectroscopy and X-ray diffraction, we find evidence that hydrogen penetrates the perovskite structure. Concomitant with this protonation, the functional properties also change, and both materials display ferroelectric-like behavior that is absent in bulk ceramics or hydrogen-free films at room temperature. We also find that thermal annealing can be used to expel the hydrogen from the membranes, which henceforth recover bulk-like properties. The two main conclusions of this work are that (i) any perovskite membrane made by sacrificial layer hydrolysis is vulnerable to hydrogen penetration (protonation) that can induce important but extrinsic changes in functional properties, and (ii) the hydrogen can, and should, be expelled by annealing to recover intrinsic behaviour.

cond-mat.mtrl-sci↗

arXiv2025

Ultrafast decoupling of polarization and strain in ferroelectric BaTiO$_3$

A fundamental understanding of the interplay between lattice structure, polarization and electrons is pivotal to the optical control of ferroelectrics. The interaction between light and matter enables the remote and wireless control of the ferroelectric polarization on the picosecond timescale, while inducing strain, i.e., lattice deformation. At equilibrium, the ferroelectric polarization is proportional to the strain, and is typically assumed to be so also out of equilibrium. Decoupling the polarization from the strain would remove the constraint of sample design and provide an effective knob to manipulate the polarization by light. Here, upon an above-bandgap laser excitation of the prototypical ferroelectric BaTiO$_3$, we induce and measure an ultrafast decoupling between polarization and strain that begins within 350 fs, by softening Ti-O bonds via charge transfer, and lasts for several tens of picoseconds. We show that the ferroelectric polarization out of equilibrium is mainly determined by photoexcited electrons, instead of the strain. This excited state could serve as a starting point to achieve stable and reversible polarization switching via THz light. Our results demonstrate a light-induced transient and reversible control of the ferroelectric polarization and offer a pathway to control by light both electric and magnetic degrees of freedom in multiferroics.

cond-mat.mtrl-sci↗

arXiv2024

Hierarchical domain structures in buckled ferroelectric free sheets

Flat elastic sheets tend to display wrinkles and folds. From pieces of clothing down to two-dimensional crystals, these corrugations appear in response to strain generated by sheet compression or stretching, thermal or mechanical mismatch with other elastic layers, or surface tension. Extensively studied in metals, polymers and, more recently, in van der Waals exfoliated layers, with the advent of thin single crystal freestanding films of complex oxides, researchers are now paying attention to novel microstructural effects induced by bending ferroelectric-ferroelastics, where polarization is strongly coupled to lattice deformation. Here we show that wrinkle undulations in BaTiO3 sheets bonded to a viscoelastic substrate transform into a buckle delamination geometry when transferred onto a rigid substrate. Using spatially resolved techniques at different scales (Raman, scanning probe and electron microscopy), we show how these delaminations in the free BaTiO3 sheets display a self-organization of ferroelastic domains along the buckle profile that strongly differs from the more studied sinusoidal wrinkle geometry. Moreover, we disclose the hierarchical distribution of a secondary set of domains induced by the misalignment of these folding structures from the preferred in-plane crystallographic orientations. Our results disclose the relevance of the morphology and orientation of buckling instabilities in ferroelectric free sheets, for the stabilization of different domain structures, pointing to new routes for domain engineering of ferroelectrics in flexible oxide sheets.

cond-mat.mtrl-sci↗

arXiv2024

Photostrictive actuators based on freestanding ferroelectric membranes

Complex oxides offer a wide range of functional properties, and recent advances in fabrication of freestanding membranes of these oxides are adding new mechanical degrees of freedom to this already rich functional ecosystem. Here, we demonstrate photoactuation in freestanding thin film resonators of ferroelectric Barium Titanate (BaTiO3) and paraelectric Strontium Titanate (SrTiO3). The free-standing films, transferred onto perforated supports, act as nano-drums, oscillating at their natural resonance frequency when illuminated by a frequency-modulated laser. The light-induced deflections in the ferroelectric BaTiO3 membranes are two orders of magnitude larger than in the paraelectric SrTiO3 ones. Time-resolved X-ray micro-diffraction under illumination and temperature-dependent and holographic interferometry provide combined evidence for the photostrictive strain in BaTiO3 originating from partial screening of ferroelectric polarization by photo-excited carriers, which decreases the tetragonality of the unit cell. These findings showcase the potential of photostrictive freestanding ferroelectric films as wireless actuators operated by light.

cond-mat.mtrl-sci↗

arXiv2021

Orbital Occupancy and Hybridization in Strained SrVO$_3$ Epitaxial Films

Oxygen packaging in transition metal oxides determines the metal-oxygen hybridization and electronic occupation at metal orbitals. Strontium vanadate (SrVO$_3$), having a single electron in a $3d$ orbital, is thought to be the simplest example of strongly correlated metallic oxides. Here, we determine the effects of epitaxial strain on the electronic properties of SrVO$_3$ thin films, where the metal-oxide sublattice is corner-connected. Using x-ray absorption and x-ray linear dichroism at the V $L_{2,3}$ and O $K$-edges, it is observed that tensile or compressive epitaxial strain change the hierarchy of orbitals within the $t_{2g}$ and $e_g$ manifolds. Data show a remarkable $2p-3d$ hybridization, as well as a strain-induced reordering of the V $3d$($t_{2g}$, $e_g$) orbitals. The latter is itself accompanied by a consequent change of hybridization that modulates the hybrid $π^*$ and $σ^*$ orbitals and the carrier population at the metal ions, challenging a rigid band picture.

cond-mat.str-el↗

arXiv2017

On the persistence of polar domains in ultrathin ferroelectric capacitors

The instability of ferroelectric ordering in ultra-thin films is one of the most important fundamental issues pertaining realization of a number of electronic devices with enhanced functionality, such as ferroelectric and multiferroic tunnel junctions or ferroelectric field effect transistors. In this paper, we investigate the polarization state of archetypal ultrathin (several nanometres) ferroelectric heterostructures: epitaxial single-crystalline BaTiO$_3$ films sandwiched between the most habitual perovskite electrodes, SrRuO$_3$, on top of the most used perovskite substrate, SrTiO$_3$. We use a combination of piezoresponse force microscopy, dielectric measurements and structural characterization to provide conclusive evidence for the ferroelectric nature of the relaxed polarization state in ultrathin BaTiO$_3$ capacitors. We show that even the high screening efficiency of SrRuO$_3$ electrodes is still insufficient to stabilize polarization in SrRuO$_3$/BaTiO$_3$/SrRuO$_3$ heterostructures at room temperature. We identify the key role of domain wall motion in determining the macroscopic electrical properties of ultrathin capacitors and discuss their dielectric response in the light of the recent interest in negative capacitance behaviour.

cond-mat.mtrl-sci↗

arXiv2016

Strain-induced perpendicular magnetic anisotropy in La$_2$CoMnO$_{6-ε}$ thin films and its dependence with film thickness

Ferromagnetic insulating La$_2$CoMnO$_{6-ε}$ (LCMO) epitaxial thin films grown on top of SrTiO$_3$ (001) substrates presents a strong magnetic anisotropy favoring the out of plane orientation of the magnetization with a strong anisotropy field ($\sim 70$ kOe for film thickness of about 15 nm) and with a coercive field of about 10 kOe. The anisotropy can be tuned by modifying the oxygen content of the film which indirectly has two effects on the unit cell: i) change of the orientation of the LCMO crystallographic axis over the substrate (from c in-plane to c out-of-plane) and ii) shrinkage of the out of plane cell parameter, which implies increasing tensile strain of the films. In contrast, LCMO films grown on (LaAlO$_3$)$_{0.3}$(Sr$_2$AlTaO$_6$)$_{0.7}$ and LaAlO$_3$ substrates (with a larger out-of-plane lattice parameter and compressive stress) display in-plane magnetic anisotropy. Thus, we link the strong magnetic anisotropy observed in La$_2$CoMnO$_{6-ε}$ to the relation between in-plane and out-of-plane parameters and so to the film stress.

cond-mat.mtrl-sci↗

arXiv2012

Competing misfit relaxation mechanisms in epitaxial correlated oxides

Strain engineering of functional properties in epitaxial thin films of strongly correlated oxides exhibiting octahedral-framework structures is hindered by the lack of adequate misfit relaxation models. Here we present unreported experimental evidences of a four-stage hierarchical development of octahedral-framework perturbations resulting from a progressive imbalance between electronic, elastic and octahedral tilting energies in La0.7Sr0.3MnO3 epitaxial thin films grown on SrTiO3 substrates. Electronic softening of the Mn - O bonds near the substrate leads to the formation of an interfacial layer clamped to the substrate with strongly degraded magnetotransport properties, i.e. the so-called dead layer, while rigid octahedral tilts become relevant at advanced growth stages without significant effects on charge transport and magnetic ordering.

cond-mat.mtrl-sci↗