Tuning electronic and magnetic properties through disorder in V2O5 nanoparticles.

We report on the synthesis and characterization of V2O5 nanoparticles grown using a sol-gel method at different calcination temperatures. We observed a surprising reduction in the optical band gap from 2.20 to 1.18 eV with increasing calcination temperature from 400 to 500 °C. Raman and X-Ray diffraction measurements indicated slight changes in the lattice parameters induced by the growth process. However, density functional theory calculations of the Rietveld-refined and pristine structures revealed that the observed optical gap reduction could not be explained by structural changes alone. By introducing oxygen vacancies to the refined structures, we could reproduce the reduction of the band gap. Our calculations also showed that the inclusion of oxygen vacancies at the vanadyl position creates a spin-polarized interband state that reduces the electronic band gap and promotes a magnetic response due to unpaired electrons. This prediction was confirmed by our magnetometry measurements, which exhibited a ferromagnetic-like behavior. Our findings suggest that oxygen vacancies play a crucial role in band gap reduction and the promotion of a ferromagnetic-like response in an otherwise paramagnetic material. This provides a promising route to engineer novel devices.

Driving magnetic domains at the nanoscale by interfacial strain-induced proximity.

We investigate the local nanoscale changes of the magnetic anisotropy of a Ni film subject to an inverse magnetostrictive effect by proximity to a V2O3 layer. Using temperature-dependent photoemission electron microscopy (PEEM) combined with X-ray magnetic circular dichroism (XMCD), direct images of the Ni spin alignment across the first-order structural phase transition (SPT) of V2O3 were obtained. We find an abrupt temperature-driven reorientation of the Ni magnetic domains across the SPT, which is associated with a large increase of the coercive field. Moreover, angular dependent ferromagnetic resonance (FMR) shows a remarkable change in the magnetic anisotropy of the Ni film across the SPT of V2O3. Micromagnetic simulations based on these results are in quantitative agreement with the PEEM data. Direct measurements of the lateral correlation length of the Ni domains from XMCD images show an increase of almost one order of magnitude at the SPT compared to room temperature, as well as a broad spatial distribution of the local transition temperatures, thus corroborating the phase coexistence of Ni anisotropies caused by the V2O3 SPT. We show that the rearrangement of the Ni domains is due to strain induced by the oxide layers' structural domains across the SPT. Our results illustrate the use of alternative hybrid systems to manipulate magnetic domains at the nanoscale, which allows for engineering of coercive fields for novel data storage architectures.

The effect of Mn2Sb2 and Mn2Sb secondary phases on magnetism in (GaMn)Sb thin films.

In this work, a detailed study of structural, electrical and magnetic characterization of (GaMn)Sb diluted magnetic semiconductors (DMS) is presented. (GaMn)Sb thin films were grown by DC magnetron co-sputtering method as an innovative procedure to fabricate III-V DMS. The presence of unusual Mn2Sb2 and Mn2Sb secondary phases, induced by substrate temperature and deposition time, were revealed through XRD measurements. Magnetization measurements allow determining crossover between a paramagnetic-like to a ferromagnetic-like behavior controlled by secondary phases. It was found that both, the magnetic remanence and magnetic coercivity, increases with substrate temperature. Interestingly, the magnetic response is paramagnetic at lower deposition times and substrate temperatures, and XRD measurements suggest the absence of Mn2Sb and Mn2Sb2 in secondary phases. For longer deposition times or higher substrate temperature, XRD shows the presence of Mn2Sb2 and Mn2Sb phases and ferromagnetic-like behavior. The DC resistivity of our samples was characterized and the carrier density was determined by Hall measurements and, in contrast with the reported in other studies, found them to be a p-type semiconductor with carrier densities as big as one order of magnitude larger than reported values. From the ferromagnetic-like samples, evidence of an anomalous Hall-effect in the sample was found, with higher magnetic saturation and a anomalous Hall conductivity of 2380 S/cm. All the results point to a contribution of the secondary phases to the overall magnetic response of the samples used, and suggest the importance of studying the formation of secondary phases in the growth of DMS, especially, for the case of (GaMn)Sb where Mn ion can have multiple oxidation states.

Strain-controlled ferromagnetism in BiFeO3 nanoparticles.

Multiferroic materials are at the core of voltage-controlled spintronic devices. Therefore, an understanding of the underlying electronic correlations and their effects associated with their complex energy landscape is an important and ongoing task. One key parameter in oxide-based perovskite multiferroics is their sensitivity to strain effects under confinement. Here, we report on the ferromagnetism induced by strain-engineering at the nanoscale on BiFeO3 (BFO) nanoparticles. By controlling synthesis parameters, we were able to modify the BFO lattice parameters up to 0.15% and as a consequence, induce ferromagnetism in otherwise antiferromagnetic bulk BFO. In order to understand the driving mechanisms behind such an effect, we performed density functional theory calculations (DFT) using the BFO parameters obtained from the experiment. We found that small distortions of the structural lattice parameters of the order of 0.01% are sufficient to induce a significant spin imbalance close to the Fermi energy at the Fe sites. This may explain the appearance of weak ferromagnetism in strained BFO thin films reported earlier and offers a new route to novel voltage-controlled spintronic devices based on multiferroic materials.

Subthreshold firing in Mott nanodevices.

Resistive switching, a phenomenon in which the resistance of a device can be modified by applying an electric field1-5, is at the core of emerging technologies such as neuromorphic computing and resistive memories6-9. Among the different types of resistive switching, threshold firing10-14 is one of the most promising, as it may enable the implementation of artificial spiking neurons7,13,14. Threshold firing is observed in Mott insulators featuring an insulator-to-metal transition15,16, which can be triggered by applying an external voltage: the material becomes conducting ('fires') if a threshold voltage is exceeded7,10-12. The dynamics of this induced transition have been thoroughly studied, and its underlying mechanism and characteristic time are well documented10,12,17,18. By contrast, there is little knowledge regarding the opposite transition: the process by which the system returns to the insulating state after the voltage is removed. Here we show that Mott nanodevices retain a memory of previous resistive switching events long after the insulating resistance has recovered. We demonstrate that, although the device returns to its insulating state within 50 to 150 nanoseconds, it is possible to re-trigger the insulator-to-metal transition by using subthreshold voltages for a much longer time (up to several milliseconds). We find that the intrinsic metastability of first-order phase transitions is the origin of this phenomenon, and so it is potentially present in all Mott systems. This effect constitutes a new type of volatile memory in Mott-based devices, with potential applications in resistive memories, solid-state frequency discriminators and neuromorphic circuits.

Control of Multiferroic properties in BiFeO3 nanoparticles.

BiFeO3 (BFO) nanoparticles (NPs) were synthesized using the sol-gel method at different calcination temperatures from 400 °C to 600 °C. XRD studies have confirmed that all BFO NPs show distorted rhombohedral crystals that match the R3c space group. We found evidence of local structural strain that develops with increasing particle size as suggested by TEM and Raman spectroscopy measurements. Magnetic measurements suggest that NPs have two distinct regimes: a ferromagnetic-like one at low temperatures and a superparamagnetic-like one at room temperature. The crossover temperature increases with NPs size, suggesting a size-dependent blocking magnetic regime. Similarly, local piezoelectric measurements at room temperature in single NP have confirmed a ferroelectric order with a NP size-dependent d33 coefficient. An analysis of both the ferroelectric and the magnetic results suggest that ferromagnetism and ferroelectricity coexist at room temperature in NPs. Our results lead to the possibility of tailoring the ferroic order in multifunctional materials by means of NP size.

Nonequilibrium Phase Precursors during a Photoexcited Insulator-to-Metal Transition in V_{2}O_{3}.

Here, we photoinduce and directly observe with x-ray scattering an ultrafast enhancement of the structural long-range order in the archetypal Mott system V_{2}O_{3}. Despite the ultrafast increase in crystal symmetry, the change of unit cell volume occurs an order of magnitude slower and coincides with the insulator-to-metal transition. The decoupling between the two structural responses in the time domain highlights the existence of a transient photoinduced precursor phase, which is distinct from the two structural phases present in equilibrium. X-ray nanoscopy reveals that acoustic phonons trapped in nanoscale twin domains govern the dynamics of the ultrafast transition into the precursor phase, while nucleation and growth of metallic domains dictate the duration of the slower transition into the metallic phase. The enhancement of the long-range order before completion of the electronic transition demonstrates the critical role the nonequilibrium structural phases play during electronic phase transitions in correlated electrons systems.

Growth-Induced In-Plane Uniaxial Anisotropy in V2O3/Ni Films.

We report on a strain-induced and temperature dependent uniaxial anisotropy in V2O3/Ni hybrid thin films, manifested through the interfacial strain and sample microstructure, and its consequences on the angular dependent magnetization reversal. X-ray diffraction and reciprocal space maps identify the in-plane crystalline axes of the V2O3; atomic force and scanning electron microscopy reveal oriented rips in the film microstructure. Quasi-static magnetometry and dynamic ferromagnetic resonance measurements identify a uniaxial magnetic easy axis along the rips. Comparison with films grown on sapphire without rips shows a combined contribution from strain and microstructure in the V2O3/Ni films. Magnetization reversal characteristics captured by angular-dependent first order reversal curve measurements indicate a strong domain wall pinning along the direction orthogonal to the rips, inducing an angular-dependent change in the reversal mechanism. The resultant anisotropy is tunable with temperature and is most pronounced at room temperature, which is beneficial for potential device applications.

Magnetic field modulated microwave spectroscopy across phase transitions and the search for new superconductors.

This article introduces magnetic field modulated microwave spectroscopy (MFMMS) as a unique and high-sensitivity technique for use in the search for new superconductors. MFMMS measures reflected microwave power as a function of temperature. The modulation induced by the external ac magnetic field enables the use of phase locked detection with the consequent sensitivity enhancement. The MFMMS signal across several prototypical structural, magnetic, and electronic transitions is investigated. A literature review on microwave absorption across superconducting transitions is included. We show that MFMMS can be used to detect superconducting transitions selectively with very high sensitivity.

Multiple avalanches across the metal-insulator transition of vanadium oxide nanoscaled junctions.

The metal-insulator transition of nanoscaled VO2 devices is drastically different from the smooth transport curves generally reported. The temperature driven transition occurs through a series of resistance jumps ranging over 2 decades in magnitude, indicating that the transition is caused by avalanches. We find a power law distribution of the jump sizes, demonstrating an inherent property of the VO2 films. We report a surprising relation between jump magnitude and device size. A percolation model captures the general transport behavior, but cannot account for the statistical behavior.