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.

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.

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.

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.

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.

Voltage-driven motion of nitrogen ions: a new paradigm for magneto-ionics.

Magneto-ionics, understood as voltage-driven ion transport in magnetic materials, has largely relied on controlled migration of oxygen ions. Here, we demonstrate room-temperature voltage-driven nitrogen transport (i.e., nitrogen magneto-ionics) by electrolyte-gating of a CoN film. Nitrogen magneto-ionics in CoN is compared to oxygen magneto-ionics in Co3O4. Both materials are nanocrystalline (face-centered cubic structure) and show reversible voltage-driven ON-OFF ferromagnetism. In contrast to oxygen, nitrogen transport occurs uniformly creating a plane-wave-like migration front, without assistance of diffusion channels. Remarkably, nitrogen magneto-ionics requires lower threshold voltages and exhibits enhanced rates and cyclability. This is due to the lower activation energy for ion diffusion and the lower electronegativity of nitrogen compared to oxygen. These results may open new avenues in applications such as brain-inspired computing or iontronics in general.

Measuring Device and Material ZT in a Thin-Film Si-Based Thermoelectric Microgenerator.

Thermoelectricity (TE) is proving to be a promising way to harvest energy for small applications and to produce a new range of thermal sensors. Recently, several thermoelectric generators (TEGs) based on nanomaterials have been developed, outperforming the efficiencies of many previous bulk generators. Here, we presented the thermoelectric characterization at different temperatures (from 50 to 350 K) of the Si thin-film based on Phosphorous (n) and Boron (p) doped thermocouples that conform to a planar micro TEG. The thermocouples were defined through selective doping by ion implantation, using boron and phosphorous, on a 100 nm thin Si film. The thermal conductivity, the Seebeck coefficient, and the electrical resistivity of each Si thermocouple was experimentally determined using the in-built heater/sensor probes and the resulting values were refined with the aid of finite element modeling (FEM). The results showed a thermoelectric figure of merit for the Si thin films of z T = 0.0093, at room temperature, which was about 12% higher than the bulk Si. In addition, we tested the thermoelectric performance of the TEG by measuring its own figure of merit, yielding a result of ZT = 0.0046 at room temperature.

Kinetic arrest of front transformation to gain access to the bulk glass transition in ultrathin films of vapour-deposited glasses.

Physical vapour deposition has emerged as the technique to obtain glasses of unbeatable stability. However, vapour deposited glasses exhibit a different transformation mechanism to ordinary glasses produced from liquid. Vapour deposited glasses of different thermodynamic stability, from ultrastable to those similar to ordinary glasses, transform into the liquid state via front propagation starting at the most mobile surfaces/interfaces, at least for the first stages of the transformation, eventually dynamiting the high thermal stability achieved for some of these glasses. A previous study showed that it was possible to avoid this transformation front by capping the films with a higher Tg material. We show here fast calorimetry measurements on TPD and IMC vapour deposited glasses capped respectively with TCTA and TPD. This capped configuration is very effective in suppressing the heterogeneous transformation of the stable glasses into the supercooled liquid and shifts the devitrification temperature to much higher values, where the bulk homogeneous mechanism becomes active. This approach may be useful to further study the bulk glass transition in thin films.

Transformation kinetics of vapor-deposited thin film organic glasses: the role of stability and molecular packing anisotropy.

While ordinary glasses transform into supercooled liquid via a homogeneous bulk mechanism, thin film glasses of higher stability transform heterogeneously by a front propagating from the surface and/or the interfaces. In this work, we use quasi-adiabatic fast scanning nanocalorimetry to determine the heat capacity of thin glassy layers of indomethacin vapor-deposited in a broad temperature range of 110 K below the glass transition temperature. Their variation in fictive temperature amounts to 40 K. We show that a propagating front is the initial transformation mechanism in all cases. Using an ad hoc surface normalization procedure we determine the corresponding growth front velocity for the whole range of deposition temperatures. Although the transformation rate changes by a factor of 10 between the most and less stable samples, the relation between the mobility of the front and the thermodynamic stability of the glass is not uniquely defined. Glasses grown above 280 K, which are at equilibrium with the supercooled liquid, present a different dependence of the growth front velocity on fictive temperature compared to glasses grown out of equilibrium at Tdep < 250 K. These glasses transform faster with increasing Tf. Our data clarify previous reports and support the evidence that the fictive temperature alone is not an absolute indicator of the properties of the glass, at least when its structure is not completely isotropic. To interpret the data, we propose that the growth front velocity depends on three terms: the mobility of the liquid at a given temperature, the mobility of the glass and the arrangement of the molecules in the glass.

Simultaneous nanocalorimetry and fast XRD measurements to study the silicide formation in Pd/a-Si bilayers.

The use of a membrane-based chip nanocalorimeter in a powder diffraction beamline is described. Simultaneous wide-angle X-ray scattering and scanning nanocalorimetric measurements are performed on a thin-film stack of palladium/amorphous silicon (Pd/a-Si) at heating rates from 0.1 to 10 K s(-1). The nanocalorimeter works under a power-compensation scheme previously developed by the authors. Kinetic and structural information of the consumed and created phases can be obtained from the combined techniques. The formation of Pd2Si produces a broad calorimetric peak that contains overlapping individual processes. It is shown that Pd consumption precedes the formation of the crystalline Pd2Si phase and that the crystallite size depends on the heating rate of the experiment.

Evaluation of growth front velocity in ultrastable glasses of indomethacin over a wide temperature interval.

Ultrastable thin film glasses transform into supercooled liquid via propagating fronts starting from the surface and/or interfaces. In this paper, we analyze the consequences of this mechanism in the interpretation of specific heat curves of ultrastable glasses of indomethacin for samples with varying thickness from 20 nm up to several microns. We demonstrate that ultrastable films above 20 nm have identical fictive temperatures and that the apparent change of onset temperature in the specific heat curves originates from the mechanism of transformation and the normalization procedure. An ad hoc surface normalization of the heat capacity yields curves which collapse into a single one irrespective of their thickness. Furthermore, we fit the surface-normalized specific heat curves with a heterogeneous transformation model to evaluate the velocity of the growth front over a much wider temperature interval than previously reported. Our data expands previous values up to Tg + 75 K, covering 12 orders of magnitude in relaxation times. The results are consistent with preceding experimental and theoretical studies. Interestingly, the mobility of the supercooled liquid in the region behind the transformation front remains constant throughout the thickness of the layers.