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.