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.

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.

Abstract Realizing the potential of oxide-based memristive devices for high-density data storage and energy-efficient computing still relies on overcoming key technical challenges, including the need for a larger number of stable resistance states, faster switching speeds, lower SET/RESET voltages, improved endurance, and reduced variability. Addressing these limitations requires innovative material design strategies. Here, we demonstrate that introducing a thin layer of oxide-ion conductor SrCoO3–x between the metal and the SrTiO3-based memristive elements, expands the number of distinguishable resistance states from ≈8 to ≈22. This modification also reduced the SET/RESET voltage by 50% and markedly improved device endurance, albeit with a trade-off of reduced state retention. To assess the performance of this architecture, we trained a two-layer fully connected neural network using the experimental SrTiO3/SrCoO3–x memristor characteristics on the MNIST handwritten digit dataset. Networks with hidden-layer sizes between 64 and 256 neurons achieved classification errors below 7%. Finally, we confirmed the transferability of this interface-engineering approach by applying it to HfOx-based devices, achieving a consistent enhancement in the resistive state window.

We report the successful growth of epitaxial layers of van der Waals (vdW) lead oxide (PbO) polymorphs on different substrates, via pulsed laser deposition. A thin layer of vdW alpha-PbO (similar to 5 nm) was subsequently used as a virtual substrate to grow thin films of perovskites BaTiO3, SrTiO3, and the spinel CoFe2O4. For some of these layers, the crystal quality or functionality was comparable to direct epitaxy on single-crystal oxide substrates. Notably, films with a larger lattice parameter underwent spontaneous and spatially uniform spalling within days of growth, remaining structurally intact, or were easily exfoliated and transferred using the tape method. This work establishes PbO as a promising virtual substrate for the fabrication of freestanding oxide membranes via vdW epitaxy, offering advantages over conventional sacrificial-layer methods.

Here we investigate epitaxial Hf0.5Zr0.5O2 ferroelectric thin films as potential candidates to be used as non-volatile electric-field-modulated thermal memories. The electric-field dependence of the thermal conductivity of metal/Hf0.5Zr0.5O2/Y2O3:ZrO2 devices is found to be hysteretic-resembling a polarization vs. electric field hysteresis loop-, reaching a maximum (minimum) at large applied positive (negative) electric fields from the top metallic electrode. This dynamic thermal response is compatible with the effects of the coupling between the ferroelectric polarization and oxygen ion migration in the Hf0.5Zr0.5O2 layer, in which the oxygen vacancies are the main phonon scattering centers and the polarization acts as an electrically active ion migration barrier that creates the hysteresis. This new mechanism enables two non-volatile states: high (ON) and low (OFF) thermal conductivity states when the electric field is removed, with an ON/OFF ratio of 1.6, which can be switched with applied voltages lower than -5 and +5 V, respectively. Both the ON and OFF states exhibit high stability over time, though the switching speed is limited by ion mobility in the Y2O3:ZrO2 electrode.

Electrically conductive two-dimensional covalent organic frameworks (2D COFs) have emerged as a versatile class of crystalline porous polymers with promising applications in electronics and energy storage. However, high electrical conductivity generally relies on post-synthetic doping to generate charge carriers, which can compromise crystallinity, porosity, and structural homogeneity. Persistent neutral radical conductors provide an attractive alternative, as their unpaired electrons can generate free charge carriers without the need for counterions. Nevertheless, the incorporation of highly spin-delocalized π-radicals into COFs remains largely unexplored. Herein, we report the design and synthesis of imine-linked 2D COFs incorporating spin-delocalized trioxotriangulene (TOT) neutral radicals through complementary synthetic approaches. Direct use of a TOT radical derivative bearing amino groups affords a highly crystalline framework (TOT-COF-H) that exhibits semiconducting behavior (σRT = 1.2 × 10-4 S cm-1), a reduced band gap (Eg = 1.09 eV), and a low activation energy (0.24 eV). This work demonstrates a viable strategy for integrating spin-delocalized neutral radical building blocks into COFs, enabling the development of intrinsically conductive, porous, and crystalline organic frameworks without the need for extrinsic doping.

Electrically conductive two-dimensional covalent organic frameworks (2D COFs) have emerged as a versatile class of crystalline porous polymers with promising applications in electronics and energy storage. However, high conductivities are typically achieved via post-synthetic doping to generate charge carriers, which can compromise crystallinity, porosity, and structural homogeneity. Persistent neutral radical conductors provide an attractive alternative, as their unpaired electrons can generate free charge carriers without the need for counterions. Nevertheless, the incorporation of highly delocalized p-radicals into COFs remains largely unexplored. Herein, we report the design and synthesis of imine-linked 2D COFs incorporating spin-delocalized trioxotriangulene (TOT) neutral radicals through two complementary synthetic approaches. Direct use of a TOT radical derivative functionalized with free amine groups affords a highly crystalline framework (TOT-COF-H) that exhibits semiconducting behavior (s RT = 1.2 × 10 -4 S cm -1 ), a reduced band gap ( E g = 1.09 eV), and low activation energy (0.24 eV). This work demonstrates a viable strategy for integrating spin-delocalized neutral radical building blocks into COFs, enabling the development of intrinsically conductive, porous, and crystalline organic frameworks without the need for extrinsic doping.

The phonon-glass electron-crystal paradigm has guided thermoelectric research in recent years. However, the inherent conflict between atomic disorder reducing phonon conduction, and the order required to maintain high electron mobility, creates a significant challenge in material design, which has driven innovation in nanostructuring and composite materials. Here, vertically aligned nanocomposites (VANs) composed of self-assembled metallic La _0.7 Sr _0.3 MnO _3 (LSMO) nanopillars in a surrounding ZnO matrix are investigated for controllable thermal conductivity. Tuning of the crystal orientation of the substrate controls the epitaxial alignment of the LSMO and ZnO phases along the horizontal and vertical interfaces. The VAN films on (111)-oriented STO substrates exhibit an increased power factor of 0.52 μ W·cm ^−1 ·K ^−2 at 600 °C beyond ZnO films of 0.15 μ W·cm ^−1 ·K ^−2 . Detailed characterization and modeling of the thermal conductivity demonstrates a reduction of about 75% as well as anisotropic behavior for the VAN films with out-of-plane and in-plane thermal conductivities of respectively 9.2 and 1.5 W·m ^−1 ·K ^−1 , in strong contrast to the isotropic behavior in ZnO films with a thermal conductivity of 38 W·m ^−1 ·K ^−1 . These results show the promising strategy of VAN thin films with a nanopillar-matrix architecture to scatter phonons and to enhance the thermoelectric performance.

The great potential of memristive devices for real-world applications still relies on overcoming key technical challenges, including the need for a larger number of stable resistance states, faster switching speeds, lower SET/RESET voltages, improved endurance, and reduced variability. One material optimization strategy that has still been quite overlooked is interface engineering, specifically, tailoring the electrode/dielectric interface to modulate oxygen exchange. Here, we demonstrate that introducing materials with high ionic mobility can significantly expand the accessible oxygen concentration range within the dielectric layer, significantly broadening the memory window. Using SrTiO3-based memristive stacks, we integrated an ion-conducting SrCoO3 interfacial layer to facilitate oxygen transfer, increasing the number of distinguishable resistance states from 8 to 22. This modification also reduced the SET/RESET voltage by 50

Here we investigate epitaxial Hf0.5Zr0.5O2 ferroelectric thin films as potential candidates to be used as non-volatile electric-field-modulated thermal memories. The electric-field dependence of the thermal conductivity of metal/Hf0.5Zr0.5O2/YSZ devices is found to be hysteretic, resembling the polarization vs electric field hysteresis loops, being maximum (minimum) at large applied positive (negative) voltages from the top metallic electrode. This dynamic thermal response is compatible with the coupling between the ferroelectric polarization and the oxygen ion migration, in which the oxygen vacancies are the main phonon scattering sources and the polarization acts as an electrically active ion migration barrier that creates the hysteresis. This new mechanism enables two non-volatile thermal states: high (ON) and low (OFF) thermal conductivity, with an ON/OFF ratio of 1.6. Both the ON and OFF states exhibit high stability over time, though the switching speed is limited by ion mobility in the YSZ electrode.

The increase in thermal conductivity, kappa, at small period lengths in covalently bonded semiconductor and oxide epitaxial superlattices (SLs) is a hallmark of coherent phonon transport and a route for improving heat dissipation in the thin limit. Here, we show that, on the contrary, the phonon coherence length remains shorter than the minimum SL period in van der Waals (vdW) SLs. We measured the cross-plane kappa(z) of epitaxial Bi2Se3/beta-In2Se3 vdW SLs grown by molecular beam epitaxy; our results show that kappa decreases monotonically with increasing interface density down to the two-layer period limit. This suggests that the weak interface vdW bonding of these SLs results in diffusive phonon transport over the whole period range. We discuss further reduction to single-layer SLs and its effects on crystal and interface quality. The results presented in this paper highlight a constraint for thermal management in vdW-based nanoelectronic and thermoelectric devices.

We present a study on the reversibility of thermal conductivity in iron oxides through topochemical oxygen exchange between brownmillerite (BM) (Ca,Sr)FeO2.5 and perovskite (PV) (Ca,Sr)FeO3.0. By using different oxidation methods, including gas phase (O2/O3), liquid phase (NaOCl in H2O), and solid electrolyte (Y2O3:ZrO2), we demonstrate that the oxidation pathway has a critical influence on the reversibility of the ionic-exchange process. Cyclic oxidation and reduction using O2/O3 or NaOCl lead to an important accumulation of structural defects, undermining the reversibility of thermal conductivity. In the case of wet oxidation, we demonstrate an inherent tendency of negative charge-transfer oxides toward amorphization and elucidate the origin of this effect. Conversely, the electrochemical injection of the O2- ions via a Y2O3:ZrO2 solid electrolyte reduces structural damage significantly, enhancing both reversibility and durability. This study underscores the importance of selecting appropriate topochemical oxygen exchange methods to maintain structural integrity and optimize functional performance in oxide-based tunable devices.

The use of magnetic garnets in new technologies such as spintronic devices requires fine-structured thin films. Classical fabrication techniques for these materials, typically physical vapor deposition methods, lead to excellent magnetic behavior. However, availability and scalability for potential applications are well restricted. In this study, we propose an innovative approach to fabricating Yttrium Iron Garnet thin films with precise thickness control achieved through iterative layer deposition via a chemical synthesis route. Remarkably, the iterative deposition process results in films exhibiting exceptional crystallinity. Magnetic characterization provides saturation magnetization and coercivity values on par with those reported in literature, summed to narrow ferromagnetic resonance lines. Therefore, in this work we demonstrate the viability of polymer assisted deposition as a promising alternative thinking about scalability to conventional deposition techniques for this material. Notably, our findings reveal energy conversion efficiencies comparable to those achieved with materials synthesized via physical vapor deposition methods.

The operation of oxide-based memristive devices relies on the fast accumulation and depletion of oxygen vacancies by an electric field close to the metal-oxide interface. Here, we show that the reversible change of the local concentration of oxygen vacancies at this interface also produces a change in the thermal boundary resistance (TBR), i.e., a thermal resistive switching effect. We used frequency domain thermoreflectance to monitor the interfacial metal-oxide TBR in (Pt,Cr)/SrTiO3 devices, showing a change of ≈20% under usual SET/RESET operation voltages, depending on the structure of the device. Time-dependent thermal relaxation experiments suggest ionic rearrangement along the whole area of the metal/oxide interface, apart from the ionic filament responsible for the electrical conductivity switching. The experiments presented in this work provide valuable knowledge about oxide ion dynamics in redox-based memristive devices.

Enhancing the switching speed of oxide-based memristive devices at a low voltage level is crucial for their use as non-volatile memory and their integration into emerging computing paradigms such as neuromorphic computing. Efforts to accelerate the switching speed often result in an energy tradeoff, leading to an increase of the minimum working voltage. In our study, we present an innovative solution: the introduction of a low thermal conductivity layer placed within the active electrode, which impedes the dissipation of heat generated during the switching process. The result is a notable acceleration in the switching speed of the memristive model system SrTiO_3 by a remarkable factor of 10^3, while preserving the integrity of the switching layer and the interfaces with the electrodes, rendering it adaptable to various filamentary memristive systems. The incorporation of HfO_2 or TaO_x as heat-blocking layers not only streamlines the fabrication process, but also ensures compatibility with complementary metal-oxide-semiconductor technology.

Phonons, the collective excitations responsible for heat transport in crystalline insulating solids, lack electric charge or magnetic moment, which complicates their active control via external fields. This presents a significant challenge in designing thermal equivalents of basic electronic circuit elements, such as transistors or diodes. Achieving these goals requires precise and reversible modification of thermal conductivity in materials. In this work, the continuous tuning of local thermal conductivity in charge-transfer SrFeO3-x and La0.6Sr0.4CoO3-x oxides using a voltage-biased Atomic Force Microscopy (AFM) tip at room temperature is demonstrated. This method allows the creation of micron-sized domains with well-defined thermal conductivity, achieving reductions of up to 50%, measured by spatially resolved Frequency Domain Thermoreflectance (FDTR). By optimizing the oxide's chemical composition, the thermal states remain stable under normal atmospheric conditions but can be reverted to their original values through thermal annealing in air. A comparison between Mott-Hubbard and charge-transfer oxides reveals the critical role of redox-active lattice oxygen in ensuring full reversibility of the process. This approach marks a significant step toward fabricating oxide-based tunable microthermal resistances and other elements for thermal circuits.

The use of copper-based artificial nucleases as potential anticancer agents has been hampered by their poor selectivity in the oxidative DNA cleavage process. An alternative strategy to solve this problem is to design systems capable of selectively damaging noncanonical DNA structures that play crucial roles in the cell cycle. We designed an oligocationic CuII peptide helicate that selectively binds and cleaves DNA three-way junctions (3WJs) and induces oxidative DNA damage via a ROS-mediated pathway both in vitro and in cellulo, specifically at DNA replication foci of the cell nucleus, where this DNA structure is transiently generated. To our knowledge, this is the first example of a targeted chemical nuclease that can discriminate with high selectivity 3WJs from other forms of DNA both in vitro and in mammalian cells. Since the DNA replication process is deregulated in cancer cells, this approach may pave the way for the development of a new class of anticancer agents based on copper-based artificial nucleases.

In magnetic tunnel junctions based on iron oxide nanoparticles the disorder and the oxidation state of the surface spin as well as the nanoparticles functionalization play a crucial role in the magnetotransport properties. In this work, we report a systematic study of the effects of vacuum annealing on the structural, magnetic and transport properties of self-assembled ∼10 nm Fe3O4nanoparticles. The high temperature treatment (from 573 to 873 K) decomposes the organic coating into amorphous carbon, reducing the electrical resistivity of the assemblies by 4 orders of magnitude. At the same time, the 3.Fe2+/(Fe3++Fe2+) ratio is reduced from 1.11 to 0.13 when the annealing temperature of the sample increases from 573 to 873 K, indicating an important surface oxidation. Although the 2 nm physical gap remains unchanged with the thermal treatment, a monotonous decrease of tunnel barrier width was obtained from the electron transport measurements when the annealing temperature increases, indicating an increment in the number of defects and hot-spots in the gap between the nanoparticles. This is reflected in the reduction of the spin dependent tunneling, which reduces the interparticle magnetoresistance. This work shows new insights about influence of the nanoparticle interfacial composition, as well their the spatial arrangement, on the tunnel transport of self-assemblies, and evidence the importance of optimizing the nanostructure fabrication for increasing the tunneling current without degrading the spin polarized current.

The development of systems that can be switched between states with different thermal conductivities is one of the current challenges in materials science. Despite their enormous diversity and chemical richness, molecular materials have been only scarcely explored in this regard. Here, we report a reversible, light-triggered thermal conductivity switching of ≈30-40% in mesophases of pure 4,4'-dialkyloxy-3-methylazobenzene. By doping a liquid crystal matrix with the azobenzene molecules, reversible and bidirectional switching of the thermal conductivity can be achieved by UV/Vis-light irradiation. Given the enormous variety of photoactive molecules and chemically compatible liquid crystal mesophases, this approach opens unforeseen possibilities for developing effective thermal switches based on molecular materials.