Porous and Meltable Metal-Organic Polyhedra for the Generation and Shaping of Porous Mixed-Matrix Composites.

Here, we report the synthesis of BCN-93, a meltable, functionalized, and permanently porous metal-organic polyhedron (MOP) and its subsequent transformation into amorphous or crystalline, shaped, self-standing, transparent porous films via melting and subsequent cooling. The synthesis entails the outer functionalization of a MOP with meltable polymer chains: in our model case, we functionalized a Rh(II)-based cuboctahedral MOP with poly(ethylene glycol). Finally, we demonstrate that once melted, BCN-93 can serve as a porous matrix into which other materials or molecules can be dispersed to form mixed-matrix composites. To illustrate this, we combined BCN-93 with one of various additives (either two MOF crystals, a porous cage, or a linear polymer) to generate a series of mixed-matrix films, each of which exhibited greater CO2 uptake relative to the parent film.

Robust multiferroicity and magnetic modulation of the ferroelectric imprint field in heterostructures comprising epitaxial Hf0.5Zr0.5O2 and Co.

Magnetoelectric multiferroics, either single-phase or composites comprising ferroelectric/ferromagnetic coupled films, are promising candidates for energy efficient memory computing. However, most of the multiferroic magnetoelectric systems studied so far are based on materials that are not compatible with industrial processes. Doped hafnia is emerging as one of the few CMOS-compatible ferroelectric materials. Thus, it is highly relevant to study the integration of ferroelectric hafnia into multiferroic systems. In particular, ferroelectricity in hafnia, and the eventual magnetoelectric coupling when ferromagnetic layers are grown atop of it, are very much dependent on quality of interfaces. Since magnetic metals frequently exhibit noticeable reactivity when grown onto oxides, it is expected that ferroelectricity and magnetoelectricity might be reduced in multiferroic hafnia-based structures. In this article, we present excellent ferroelectric endurance and retention in epitaxial Hf0.5Zr0.5O2 films grown on buffered silicon using Co as the top electrode. The crucial influence of a thin Pt capping layer grown on top of Co on the ferroelectric functional characteristics is revealed by contrasting the utilization of Pt-capped Co, non-capped Co and Pt. Magnetic control of the imprint electric field (up to 40% modulation) is achieved in Pt-capped Co/Hf0.5Zr0.5O2 structures, although this does not lead to appreciable tuning of the ferroelectric polarization, as a result of its high stability. Computation of piezoelectric and flexoelectric strain-mediated mechanisms of the observed magnetoelectric coupling reveal that flexoelectric contributions are likely to be at the origin of the large imprint electric field variation.

Reversible optical control of magnetism in engineered artificial multiferroics.

Optical means instead of electric fields may offer a new pathway for low-power and wireless control of magnetism, holding great potential to design next-generation memory and spintronic devices. Artificial multiferroic materials have shown remarkable suitability as platforms towards the optical control of magnetic properties. However, the practical use of magnetic modulation should be both stable and reversible and, particularly, it should occur at room temperature. Here we show an unprecedented reversible modulation of magnetism using low-intensity visible-light in Fe75Al25/BaTiO3 heterostructures, at room temperature. This is enabled by the existence of highly oriented charged domain walls arranged in arrays of alternating in-plane and out-of-plane ferroelectric domains with stripe morphology. Light actuation yields a net anisotropic stress caused by ferroelectric domain switching, which leads to a 90-degree reorientation of the magnetic easy axis. Significant changes in the coercivity and squareness ratio of the hysteresis loops can be light-modulated, encouraging the development of novel low energy-consumption wireless magneto-optical devices.

Enhanced Proliferation and Differentiation of Human Osteoblasts by Remotely Controlled Magnetic-Field-Induced Electric Stimulation Using Flexible Substrates.

With the progressive aging of the population, bone fractures are an increasing major health concern. Diverse strategies are being studied to reduce the recovery times using nonaggressive treatments. Electrical stimulation (either endogenous or externally applied electric pulses) has been found to be effective in accelerating bone cell proliferation and differentiation. However, the direct insertion of electrodes into tissues can cause undesirable inflammation or infection reactions. As an alternative, magnetoelectric heterostructures (wherein magnetic fields are applied to induce electric polarization) could be used to achieve electric stimulation without the need for implanted electrodes. Here, we develop a magnetoelectric platform based on flexible kapton/FeGa/P(VDF-TrFE) (flexible substrate/magnetostrictive layer/ferroelectric layer) heterostructures for remote magnetic-field-induced electric field stimulation of human osteoblast cells. We show that the use of flexible supports overcomes the clamping effects that typically occur when analogous magnetoelectric structures are grown onto rigid substrates (which preclude strain transfer from the magnetostrictive to the ferroelectric layers). The study of the diverse proliferation and differentiation markers evidence that in all the stages of bone formation (cell proliferation, extracellular matrix maturation, and mineralization), the electrical stimulation of the cells results in a remarkably better performance. The results pave the way for novel strategies for remote cell stimulation based on flexible platforms not only in bone regeneration but also in many other applications where electrical cell stimulation may be beneficial (e.g., neurological diseases or skin regeneration).

Wireless magneto-ionics: voltage control of magnetism by bipolar electrochemistry.

Modulation of magnetic properties through voltage-driven ion motion and redox processes, i.e., magneto-ionics, is a unique approach to control magnetism with electric field for low-power memory and spintronic applications. So far, magneto-ionics has been achieved through direct electrical connections to the actuated material. Here we evidence that an alternative way to reach such control exists in a wireless manner. Induced polarization in the conducting material immersed in the electrolyte, without direct wire contact, promotes wireless bipolar electrochemistry, an alternative pathway to achieve voltage-driven control of magnetism based on the same electrochemical processes involved in direct-contact magneto-ionics. A significant tunability of magnetization is accomplished for cobalt nitride thin films, including transitions between paramagnetic and ferromagnetic states. Such effects can be either volatile or non-volatile depending on the electrochemical cell configuration. These results represent a fundamental breakthrough that may inspire future device designs for applications in bioelectronics, catalysis, neuromorphic computing, or wireless communications.

Regulating Oxygen Ion Transport at the Nanoscale to Enable Highly Cyclable Magneto-Ionic Control of Magnetism.

Magneto-ionics refers to the control of magnetic properties of materials through voltage-driven ion motion. To generate effective electric fields, either solid or liquid electrolytes are utilized, which also serve as ion reservoirs. Thin solid electrolytes have difficulties in (i) withstanding high electric fields without electric pinholes and (ii) maintaining stable ion transport during long-term actuation. In turn, the use of liquid electrolytes can result in poor cyclability, thus limiting their applicability. Here we propose a nanoscale-engineered magneto-ionic architecture (comprising a thin solid electrolyte in contact with a liquid electrolyte) that drastically enhances cyclability while preserving sufficiently high electric fields to trigger ion motion. Specifically, we show that the insertion of a highly nanostructured (amorphous-like) Ta layer (with suitable thickness and electric resistivity) between a magneto-ionic target material (i.e., Co3O4) and the liquid electrolyte increases magneto-ionic cyclability from <30 cycles (when no Ta is inserted) to more than 800 cycles. Transmission electron microscopy together with variable energy positron annihilation spectroscopy reveals the crucial role of the generated TaOx interlayer as a solid electrolyte (i.e., ionic conductor) that improves magneto-ionic endurance by proper tuning of the types of voltage-driven structural defects. The Ta layer is very effective in trapping oxygen and hindering O2- ions from moving into the liquid electrolyte, thus keeping O2- motion mainly restricted between Co3O4 and Ta when voltage of alternating polarity is applied. We demonstrate that this approach provides a suitable strategy to boost magneto-ionics by combining the benefits of solid and liquid electrolytes in a synergetic manner.

Electrochemical Synthesis, Magnetic and Optical Characterisation of FePd Dense and Mesoporous Nanowires.

Dense and mesoporous FePd nanowires (NWs) with 45 to 60 at.% Pd content were successfully fabricated by template- and micelle-assisted pulsed potentiostatic electrodeposition using nanoporous anodic alumina and polycarbonate templates of varying pore sizes. An FePd electrolyte was utilized for obtaining dense NWs while a block copolymer, P-123, was added to this electrolyte as the micelle-forming surfactant to produce mesoporous NWs. The structural and magnetic properties of the NWs were investigated by electron microscopy, X-ray diffraction, and vibrating sample magnetometry. The as-prepared NWs were single phase with a face-centered cubic structure exhibiting 3.1 µm to 7.1 µm of length. Mesoporous NWs revealed a core-shell structure where the porosity was only witnessed in the internal volume of the NW while the outer surface remained non-porous. Magnetic measurements revealed that the samples displayed a soft ferromagnetic behavior that depended on the shape anisotropy and the interwire dipolar interactions. The mesoporous core and dense shell structure of the NWs were seen to be slightly affecting the magnetic properties. Moreover, mesoporous NWs performed excellently as SERS substrates for the detection of 4,4'-bipyridine, showing a low detection limit of 10-12 M. The signal enhancement can be attributed to the mesoporous morphology as well as the close proximity of the embedded NWs being conducive to localized surface plasmon resonance.

Surface Modified ß-Ti-18Mo-6Nb-5Ta (wt%) Alloy for Bone Implant Applications: Composite Characterization and Cytocompatibility Assessment.

Commercially available titanium alloys such as Ti-6Al-4V are established in clinical use as load-bearing bone implant materials. However, concerns about the toxic effects of vanadium and aluminum have prompted the development of Al- and V-free ß-Ti alloys. Herein, a new alloy composed of non-toxic elements, namely Ti-18Mo-6Nb-5Ta (wt%), has been fabricated by arc melting. The resulting single ß-phase alloy shows improved mechanical properties (Young's modulus and hardness) and similar corrosion behavior in simulated body fluid when compared with commercial Ti-6Al-4V. To increase the cell proliferation capability of the new biomaterial, the surface of Ti-18Mo-6Nb-5Ta was modified by electrodepositing calcium phosphate (CaP) ceramic layers. Coatings with a Ca/P ratio of 1.47 were obtained at pulse current densities, -jc, of 1.8-8.2 mA/cm2, followed by 48 h of NaOH post-treatment. The thickness of the coatings has been measured by scanning electron microscopy from an ion beam cut, resulting in an average thickness of about 5 µm. Finally, cytocompatibility and cell adhesion have been evaluated using the osteosarcoma cell line Saos-2, demonstrating good biocompatibility and enhanced cell proliferation on the CaP-modified Ti-18Mo-6Nb-5Ta material compared with the bare alloy, even outperforming their CaP-modified Ti-6-Al-4V counterparts.

Efficient Tumor Eradication at Ultralow Drug Concentration via Externally Controlled and Boosted Metallic Iron Magnetoplasmonic Nanocapsules.

With the aim to locally enhance the efficacy of cancer nanotherapies, here we present metal iron based magnetoplasmonic drug-loaded nanocapsules (MAPSULES), merging powerful external magnetic concentration in the tumor and efficient photothermal actuation to locally boost the drug therapeutic action at ultralow drug concentrations. The MAPSULES are composed of paclitaxel-loaded polylactic-co-glycolic acid (PLGA) nanoparticles partially coated by a nanodome shape iron/silica semishell. The iron semishell has been designed to present a ferromagnetic vortex for incorporating a large quantity of ferromagnetic material while maintaining high colloidal stability. The large iron semishell provides very strong magnetic manipulation via magnetophoretic forces, enabling over 10-fold higher trapping efficiency in microfluidic channels than typical superparamagnetic iron oxide nanoparticles. Moreover, the iron semishell exhibits highly damped plasmonic behavior, yielding intense broadband absorbance in the near-infrared biological windows and photothermal efficiency similar to the best plasmonic nanoheaters. The in vivo therapeutic assays in a mouse xenograft tumor model show a high amplification of the therapeutic effects by combining magnetic concentration and photothermal actuation in the tumor, leading to a complete eradication of the tumors at ultralow nanoparticle and drug concentration (equivalent to only 1 mg/kg PLGA nanoparticles containing 8 µg/kg of paclitaxel, i.e., 100-500-fold lower than the therapeutic window of the free and PLGA encapsulated drug and 13-3000-fold lower than current nanotherapies combining paclitaxel and light actuation). These results highlight the strength of this externally controlled and amplified therapeutic approach, which could be applied to locally boost a wide variety of drugs for different diseases.

Frequency-dependent stimulated and post-stimulated voltage control of magnetism in transition metal nitrides: towards brain-inspired magneto-ionics.

Magneto-ionics, which deals with the change of magnetic properties through voltage-driven ion migration, is expected to be one of the emerging technologies to develop energy-efficient spintronics. While a precise modulation of magnetism is achieved when voltage is applied, much more uncontrolled is the spontaneous evolution of magneto-ionic systems upon removing the electric stimuli (i.e., post-stimulated behavior). Here, we demonstrate a voltage-controllable N ion accumulation effect at the outer surface of CoN films adjacent to a liquid electrolyte, which allows for the control of magneto-ionic properties both during and after voltage pulse actuation (i.e., stimulated and post-stimulated behavior, respectively). This effect, which takes place when the CoN film thickness is below 50 nm and the voltage pulse frequency is at least 100 Hz, is based on the trade-off between generation (voltage ON) and partial depletion (voltage OFF) of ferromagnetism in CoN by magneto-ionics. This novel effect may open opportunities for new neuromorphic computing functions, such as post-stimulated neural learning under deep sleep.

Enhancing magneto-ionic effects in cobalt oxide films by electrolyte engineering.

Electric-field-driven ion motion to tailor magnetic properties of materials (magneto-ionics) offers much promise in the pursuit of voltage-controlled magnetism for highly energy-efficient spintronic devices. Electrolyte gating is a relevant means to create intense electric fields at the interface between magneto-ionic materials and electrolytes through the so-called electric double layer (EDL). Here, improved magneto-ionic performance is achieved in electrolyte-gated cobalt oxide thin films with the addition of inorganic salts (potassium iodide, potassium chloride, and calcium tetrafluoroborate) to anhydrous propylene carbonate (PC) electrolyte. Ab initio molecular dynamics simulations of the EDL structure show that K+ is preferentially located on the cobalt oxide surface and KI (when compared to KCl) favors the accumulation of positive charge close to the surface. It is demonstrated that room temperature magneto-ionics in cobalt oxide thin films is dramatically enhanced in KI-containing PC electrolyte at an optimum concentration, leading to 11-fold increase of generated magnetization and 35-fold increase of magneto-ionic rate compared to bare PC.

From Binary to Ternary Transition-Metal Nitrides: A Boost toward Nitrogen Magneto-Ionics.

Magneto-ionics is an emerging actuation mechanism to control the magnetic properties of materials via voltage-driven ion motion. This effect largely relies on the strength and penetration of the induced electric field into the target material, the amount of generated ion transport pathways, and the ionic mobility inside the magnetic media. Optimizing all these factors in a simple way is a huge challenge, although highly desirable for technological applications. Here, we demonstrate that the introduction of suitable transition-metal elements to binary nitride compounds can drastically boost magneto-ionics. More specifically, we show that the attained magneto-ionic effects in CoN films (i.e., saturation magnetization, toggling speeds, and cyclability) can be drastically enhanced through 10% substitution of Co by Mn in the thin-film composition. Incorporation of Mn leads to transformation from nanocrystalline into amorphous-like structures, as well as from metallic to semiconducting behaviors, resulting in an increase of N-ion transport channels. Ab initio calculations reveal a lower energy barrier for CoMn-N compared to Co-N that provides a fundamental understanding of the crucial role of Mn addition in the voltage-driven magnetic effects. These results constitute an important step forward toward enhanced voltage control of magnetism via electric field-driven ion motion.

Nanocomposite Materials: A Section of Nanomaterials.

"Nanocomposite materials" is one of the main sections of Nanomaterials and it has contributed with more than 440 publications during the last two years to increase the reputation and recognition of the journal by the scientific community [...].

Dynamic electric-field-induced magnetic effects in cobalt oxide thin films: towards magneto-ionic synapses.

Voltage control of magnetism via electric-field-driven ion migration (magneto-ionics) has generated intense interest due to its potential to greatly reduce heat dissipation in a wide range of information technology devices, such as magnetic memories, spintronic systems or artificial neural networks. Among other effects, oxygen ion migration in transition-metal-oxide thin films can lead to the generation or full suppression of controlled amounts of ferromagnetism ('ON-OFF' magnetic transitions) in a non-volatile and fully reversible manner. However, oxygen magneto-ionic rates at room temperature are generally considered too slow for industrial applications. Here, we demonstrate that sub-second ON-OFF transitions in electrolyte-gated paramagnetic cobalt oxide films can be achieved by drastically reducing the film thickness from >200 nm down to 5 nm. Remarkably, cumulative magneto-ionic effects can be generated by applying voltage pulses at frequencies as high as 100 Hz. Neuromorphic-like dynamic effects occur at these frequencies, including potentiation (cumulative magnetization increase), depression (i.e., partial recovery of magnetization with time), threshold activation, and spike time-dependent magnetic plasticity (learning and forgetting capabilities), mimicking many of the biological synapse functions. The systems under investigation show features that could be useful for the design of artificial neural networks whose magnetic properties would be governed with voltage.

Full-bandwidth electrophysiology of seizures and epileptiform activity enabled by flexible graphene microtransistor depth neural probes.

Mapping the entire frequency bandwidth of brain electrophysiological signals is of paramount importance for understanding physiological and pathological states. The ability to record simultaneously DC-shifts, infraslow oscillations (<0.1 Hz), typical local field potentials (0.1-80 Hz) and higher frequencies (80-600 Hz) using the same recording site would particularly benefit preclinical epilepsy research and could provide clinical biomarkers for improved seizure onset zone delineation. However, commonly used metal microelectrode technology suffers from instabilities that hamper the high fidelity of DC-coupled recordings, which are needed to access signals of very low frequency. In this study we used flexible graphene depth neural probes (gDNPs), consisting of a linear array of graphene microtransistors, to concurrently record DC-shifts and high-frequency neuronal activity in awake rodents. We show here that gDNPs can reliably record and map with high spatial resolution seizures, pre-ictal DC-shifts and seizure-associated spreading depolarizations together with higher frequencies through the cortical laminae to the hippocampus in a mouse model of chemically induced seizures. Moreover, we demonstrate the functionality of chronically implanted devices over 10 weeks by recording with high fidelity spontaneous spike-wave discharges and associated infraslow oscillations in a rat model of absence epilepsy. Altogether, our work highlights the suitability of this technology for in vivo electrophysiology research, and in particular epilepsy research, by allowing stable and chronic DC-coupled recordings.

Editorial for the Special Issue on "10th Anniversary of Nanomaterials-Recent Advances in Nanocomposite Thin Films and 2D Materials".

As a way to celebrate the 10th anniversary of the journal Nanomaterials, this Special Issue within the section 'Nanocomposite thin film and 2D materials' provides an overview of the wide spectrum of research challenges and applications in the field, represented by a collection of 12 contributions, including three up-to-date review articles plus nine original works, in different targeted topics as described below [...].

Magneto-Ionics in Single-Layer Transition Metal Nitrides.

Magneto-ionics allows for tunable control of magnetism by voltage-driven transport of ions, traditionally oxygen or lithium and, more recently, hydrogen, fluorine, or nitrogen. Here, magneto-ionic effects in single-layer iron nitride films are demonstrated, and their performance is evaluated at room temperature and compared with previously studied cobalt nitrides. Iron nitrides require increased activation energy and, under high bias, exhibit more modest rates of magneto-ionic motion than cobalt nitrides. Ab initio calculations reveal that, based on the atomic bonding strength, the critical field required to induce nitrogen-ion motion is higher in iron nitrides (≈6.6 V nm-1) than in cobalt nitrides (≈5.3 V nm-1). Nonetheless, under large bias (i.e., well above the magneto-ionic onset and, thus, when magneto-ionics is fully activated), iron nitride films exhibit enhanced coercivity and larger generated saturation magnetization, surpassing many of the features of cobalt nitrides. The microstructural effects responsible for these enhanced magneto-ionic effects are discussed. These results open up the potential integration of magneto-ionics in existing nitride semiconductor materials in view of advanced memory system architectures.

ZnO Nanosheet-Coated TiZrPdSiNb Alloy as a Piezoelectric Hybrid Material for Self-Stimulating Orthopedic Implants.

A Ti-based alloy (Ti45Zr15Pd30Si5Nb5) with already proven excellent mechanical and biocompatibility features has been coated with piezoelectric zinc oxide (ZnO) to induce the electrical self-stimulation of cells. ZnO was grown onto the pristine alloy in two different morphologies: a flat dense film and an array of nanosheets. The effect of the combined material on osteoblasts (electrically stimulable cells) was analyzed in terms of proliferation, cell adhesion, expression of differentiation markers and induction of calcium transients. Although both ZnO structures were biocompatible and did not induce inflammatory response, only the array of ZnO nanosheets was able to induce calcium transients, which improved the proliferation of Saos-2 cells and enhanced the expression of some early differentiation expression genes. The usual motion of the cells imposes strain to the ZnO nanosheets, which, in turn, create local electric fields owing to their piezoelectric character. These electric fields cause the opening of calcium voltage gates and boost cell proliferation and early differentiation. Thus, the modification of the Ti45Zr15Pd30Si5Nb5 surface with an array of ZnO nanosheets endows the alloy with smart characteristics, making it capable of electric self-stimulation.

Full Optimization of an Electroless Nickel Solution: Boosting the Performance of Low-Phosphorous Coatings.

Univariate and multivariate optimizations of a novel electroless nickel formulation have been carried out by means of the Taguchi method. From the compositional point of view, adjustment of the complexing agent concentration in solution is crucial for fine-tuning free Ni2+ ions concentration and, in turn, the mechanical properties of the resulting coatings. The Ni (II) concentration and the pH are the main parameters which help restrict the incorporation of phosphorous into the Ni layers. On the other hand, the stirring rate, the pH and the reducing agent concentration are the most influential parameters for the corrosion resistance of the coatings. Multivariate optimization of the electrolyte leads to a set of optimized parameters in which the mechanical properties (hardness and worn volume) of the layers are similar to the optimal values achieved in the univariate optimization, but the corrosion rate is decreased by one order of magnitude.

Electroless Palladium-Coated Polymer Scaffolds for Electrical Stimulation of Osteoblast-Like Saos-2 Cells.

Three-dimensional porous scaffolds offer some advantages over conventional treatments for bone tissue engineering. Amongst all non-bioresorbable scaffolds, biocompatible metallic scaffolds are preferred over ceramic and polymeric scaffolds, as they can be used as electrodes with different electric field intensities (or voltages) for electric stimulation (ES). In the present work we have used a palladium-coated polymeric scaffold, generated by electroless deposition, as a bipolar electrode to electrically stimulate human osteoblast-like Saos-2 cells. Cells grown on palladium-coated polyurethane foams under ES presented higher proliferation than cells grown on foams without ES for up to 14 days. In addition, cells grown in both conditions were well adhered, with a flat appearance and a typical actin cytoskeleton distribution. However, after 28 days in culture, cells without ES were filling the entire structure, while cells under ES appeared rounded and not well adhered, a sign of cell death onset. Regarding osteoblast differentiation, ES seems to enhance the expression of early expressed genes. The results suggest that palladium-coated polyurethane foams may be good candidates for osteoblast scaffolds and demonstrate that ES enhances osteoblast proliferation up to 14 days and upregulate expression genes related to extracellular matrix formation.