Spin-to-Charge Conversion in All-Oxide La2/3Sr1/3MnO3/SrIrO3 Heterostructures.

Spin injection and spin-charge conversion processes in all-oxide La2/3Sr1/3MnO3/SrIrO3 (LSMO/SIO) heterostructures with different SIO layer thickness and interfacial features have been studied. Ferromagnetic resonance (FMR) technique has been used to generate pure spin currents by spin pumping (SP) in ferromagnetic (FM) half-metallic LSMO. The change of the resonance linewidth in bare LSMO layers and LSMO/SIO heterostructures suggests a successful spin injection into the SIO layers. However, low values of the spin mixing conductance, compared to more traditional permalloy (Py)/Pt or yttrium iron garnet (YIG)/Pt systems, are found. A thorough analysis of the interfaces by high-resolution scanning transmission electron microscopy (HR-STEM) imaging suggests that they are structurally clean and atomic sharp, but a compositional analysis by energy-dispersive X-ray spectroscopy (EDS) reveals the interdiffusion of La, Ir, and Mn atomic species in the first atomic layers close to the interface. Inverse spin Hall effect (ISHE) measurements evidence that interfacial features play a very relevant role in controlling the effectiveness of the spin injection process and low transversal ISHE voltage signals are detected. In addition, it is found that larger voltage signals are detected for the lowest SIO layer thickness highlighting the role of the spin diffusion length (λsd)/SIO layer thickness ratio. The values of ISHE voltage are rather low but allow us to determine the spin Hall angle of SIO (θSH ≈ 1.12% at T = 250 K), which is remarkably similar to that obtained for the well-known Py/Pt system, therefore suggesting that SIO could be a promising spin-Hall material.

Long-Term Performance of Magnetic Force Microscopy Tips Grown by Focused Electron Beam Induced Deposition.

High-resolution micro- and nanostructures can be grown using Focused Electron Beam Induced Deposition (FEBID), a direct-write, resist-free nanolithography technology which allows additive patterning, typically with sub-100 nm lateral resolution, and down to 10 nm in optimal conditions. This technique has been used to grow magnetic tips for use in Magnetic Force Microscopy (MFM). Due to their high aspect ratio and good magnetic behavior, these FEBID magnetic tips provide several advantages over commercial magnetic tips when used for simultaneous topographical and magnetic measurements. Here, we report a study of the durability of these excellent candidates for high-resolution MFM measurements. A batch of FEBID-grown magnetic tips was subjected to a systematic analysis of MFM magnetic contrast for 30 weeks, using magnetic storage tape as a test specimen. Our results indicate that these FEBID magnetic tips operate effectively over a long period of time. The magnetic signal was well preserved, with a maximum reduction of 60% after 21 weeks of recurrent use. No significant contrast degradation was observed after 30 weeks in storage.

Spin Glass State in Strained La2/3Ca1/3MnO3 Thin Films.

Epitaxial strain modifies the physical properties of thin films deposited on single-crystal substrates. In a previous work, we demonstrated that in the case of La2/3Ca1/3MnO3 thin films the strain induced by the substrate can produce the segregation of a non-ferromagnetic layer (NFL) at the top surface of ferromagnetic epitaxial La2/3Ca1/3MnO3 for a critical value of the tetragonality τ, defined as τ = |c - a|a, of τC ≈ 0.024. Although preliminary analysis suggested its antiferromagnetic nature, to date a complete characterization of the magnetic state of such an NFL has not been performed. Here, we present a comprehensive magnetic characterization of the strain-induced segregated NFL. The field-cooled magnetic hysteresis loops exhibit an exchange bias mechanism below T ≈ 80 K, which is well below the Curie temperature of the ferromagnetic La2/3Ca1/3MnO3 layer. The exchange bias and coercive fields decay exponentially with temperature, which is commonly accepted to describe spin-glass (SG) behavior. The signatures of slow dynamics were confirmed by slow spin relaxation over a wide temperature regime. Low-energy muon spectroscopy experiments directly evidence the slowing down of the magnetic moments below ~100 K in the NFL. The experimental results indicate the SG nature of the NFL. This SG state can be understood within the context of the competing ferromagnetic and antiferromagnetic interactions of similar energies.

Effect of Ethylene Glycol: Citric Acid Molar Ratio and pH on the Morphology, Vibrational, Optical and Electronic Properties of TiO2 and CuO Powders Synthesized by Pechini Method.

High-purity TiO2 and CuO powders were synthesized by the Pechini method, an inexpensive and easy-to-implement procedure to synthetize metal oxides. The variables of synthesis were the ethylene glycol:citric acid molar ratio and the pH. High reproducibility of the anatase and tenorite phase was obtained for all synthesis routes. The degree of purity of the powders was confirmed by XRD, FTIR, UV-Vis absorption and XPS spectra. SEM and TEM images revealed the powders are composed of micrometer grains that can have a spherical shape (only in the TiO2) or formed by a non-compacted nanocrystalline conglomerate. FTIR spectra only displayed vibrational modes associating TiO2 and CuO with nanoparticle behavior. UV-Vis absorption spectra revealed the values of maximum absorbance percentage of both systems are reached in the ultraviolet region, with percentages above 83% throughout the entire visible light spectrum for the CuO system, a relevant result for solar cell applications. Finally, XPS experiments allow the observation of the valence bands and the calculation of the energy bands of all oxides.

Direct Epitaxial Growth of Polar Hf0.5Zr0.5O2 Films on Corundum.

Single-phase epitaxial Hf0.5Zr0.5O2 films with non-centrosymmetric orthorhombic structure have been grown directly on electrode-free corundum (α-Al2O3) substrates by pulsed laser deposition. A combination of high-resolution X-ray diffraction and X-ray absorption spectroscopy confirms the epitaxial growth of high-quality films belonging to the Pca21 space group, with [111] out-of-plane orientation. The surface of a 7-nm-thick sample exhibits an atomic step-terrace structure with a corrugation of the order of one atomic layer, as proved by atomic force microscopy. Scanning transmission electron microscopy reveals that it consists of grains with around 10 nm lateral size. The polar nature of this film has been corroborated by pyroelectric measurements. These results shed light on the mechanisms of the epitaxial stabilization of the ferroelectric phase of hafnia.

Relaxation Mechanisms and Strain-Controlled Oxygen Vacancies in Epitaxial SrMnO3 Films.

SrMnO3 has a rich epitaxial strain-dependent ferroic phase diagram, in which a variety of magnetic orderings, even ferroelectricity, and thus multiferroicity, are accessible by gradually modifying the strain. Different relaxation processes, though, including the presence of strain-induced oxygen vacancies, can severely curtail the possibility of stabilizing these ferroic phases. Here, we report on a thorough investigation of the strain relaxation mechanisms in SrMnO3 films grown on several substrates imposing varying degrees of strain from slightly compressive (-0.39%) to largely tensile ≈+3.8%. First, we determine the strain dependency of the critical thickness (t c) below which pseudomorphic growth is obtained. Second, the mechanisms of stress relaxation are elucidated, revealing that misfit dislocations and stacking faults accommodate the strain above t c. Yet, even for films thicker than t c, the atomic monolayers below t c are proved to remain fully coherent. Therefore, multiferroicity may also emerge even in films that appear to be partially relaxed. Last, we demonstrate that fully coherent films with the same thickness present a lower oxygen content for increasing tensile mismatch with the substrate. This behavior proves the coupling between the formation of oxygen vacancies and epitaxial strain, in agreement with first-principles calculations, enabling the strain control of the Mn3+/Mn4+ ratio, which strongly affects the magnetic and electrical properties. However, the presence of oxygen vacancies/Mn3+ cations reduces the effective epitaxial strain in the SrMnO3 films and, thus, the accessibility to the strain-induced multiferroic phase.

Crystal engineering and ferroelectricity at the nanoscale in epitaxial 1D manganese oxide on silicon.

Ferroelectric oxides have attracted much attention due to their wide range of applications, particularly in electronic devices such as nonvolatile memories and tunnel junctions. As a result, the monolithic integration of these materials into silicon technology and their nanostructuration to develop alternative cost-effective processes are among the central points in the current technology. In this work, we used a chemical route to obtain nanowire thin films of a novel Sr1+δMn8O16 (SMO) hollandite-type manganese oxide on silicon. Scanning transmission electron microscopy combined with crystallographic computing reveals a crystal structure comprising hollandite and pyrolusite units sharing the edges of their MnO6 octahedra, resulting in three types of tunnels arranged along the c axis, where the ordering of the Sr atoms produces natural symmetry breaking. The novel structure gives rise to ferroelectricity and piezoelectricity, as revealed by local direct piezoelectric force microscopy measurements, which confirmed the ferroelectric nature of the SMO nanowire thin films at room temperature and showed a piezoelectric coefficient d33 value of 22 ± 6 pC N-1. Moreover, we proved that flexible vertical SMO nanowires can be harvested providing an electrical output energy through the piezoelectric effect, showing excellent deformability and high interface recombination. This work indicates the possibility of engineering the integration of 1D manganese oxides on silicon, a step which precedes the production of microelectronic devices.

Focused-Electron-Beam Engineering of 3D Magnetic Nanowires.

Focused-electron-beam-induced deposition (FEBID) is the ultimate additive nanofabrication technique for the growth of 3D nanostructures. In the field of nanomagnetism and its technological applications, FEBID could be a viable solution to produce future high-density, low-power, fast nanoelectronic devices based on the domain wall conduit in 3D nanomagnets. While FEBID has demonstrated the flexibility to produce 3D nanostructures with almost any shape and geometry, the basic physical properties of these out-of-plane deposits are often seriously degraded from their bulk counterparts due to the presence of contaminants. This work reviews the experimental efforts to understand and control the physical processes involved in 3D FEBID growth of nanomagnets. Co and Fe FEBID straight vertical nanowires have been used as benchmark geometry to tailor their dimensions, microstructure, composition and magnetism by smartly tuning the growth parameters, post-growth purification treatments and heterostructuring.

Metallic Diluted Dimerization in VO2 Tweeds.

The observation of electronic phase separation textures in vanadium dioxide, a prototypical electron-correlated oxide, has recently added new perspectives on the long standing debate about its metal-insulator transition and its applications. Yet, the lack of atomically resolved information on phases accompanying such complex patterns still hinders a comprehensive understanding of the transition and its implementation in practical devices. In this work, atomic resolution imaging and spectroscopy unveils the existence of ferroelastic tweed structures on ≈5 nm length scales, well below the resolution limit of currently used spectroscopic imaging techniques. Moreover, density functional theory calculations show that this pretransitional fine-scale tweed, which on average looks and behaves like the standard metallic rutile phase, is in fact weaved by semi-dimerized chains of vanadium in a new monoclinic phase that represents a structural bridge to the monoclinic insulating ground state. These observations provide a multiscale perspective for the interpretation of existing data, whereby phase coexistence and structural intermixing can occur all the way down to the atomic scale.

Highly-efficient growth of cobalt nanostructures using focused ion beam induced deposition under cryogenic conditions: application to electrical contacts on graphene, magnetism and hard masking.

Emergent technologies are required in the field of nanoelectronics for improved contacts and interconnects at nano and micro-scale. In this work, we report a highly-efficient nanolithography process for the growth of cobalt nanostructures requiring an ultra-low charge dose (15 µC cm-2, unprecedented in single-step charge-based nanopatterning). This resist-free process consists in the condensation of a ∼28 nm-thick Co2(CO)8 layer on a substrate held at -100 °C, its irradiation with a Ga+ focused ion beam, and substrate heating up to room temperature. The resulting cobalt-based deposits exhibit sub-100 nm lateral resolution, display metallic behaviour (room-temperature resistivity of 200 µΩ cm), present ferromagnetic properties (magnetization at room temperature of 400 emu cm-3) and can be grown in large areas. To put these results in perspective, similar properties can be achieved by room-temperature focused ion beam induced deposition and the same precursor only if a 2 × 103 times higher charge dose is used. We demonstrate the application of such an ultra-fast growth process to directly create electrical contacts onto graphene ribbons, opening the route for a broad application of this technology to any 2D material. In addition, the application of these cryo-deposits for hard masking is demonstrated, confirming its structural functionality.

Artificial Double-Helix for Geometrical Control of Magnetic Chirality.

Chirality plays a major role in nature, from particle physics to DNA, and its control is much sought-after due to the scientific and technological opportunities it unlocks. For magnetic materials, chiral interactions between spins promote the formation of sophisticated swirling magnetic states such as skyrmions, with rich topological properties and great potential for future technologies. Currently, chiral magnetism requires either a restricted group of natural materials or synthetic thin-film systems that exploit interfacial effects. Here, using state-of-the-art nanofabrication and magnetic X-ray microscopy, we demonstrate the imprinting of complex chiral spin states via three-dimensional geometric effects at the nanoscale. By balancing dipolar and exchange interactions in an artificial ferromagnetic double-helix nanostructure, we create magnetic domains and domain walls with a well-defined spin chirality, determined solely by the chiral geometry. We further demonstrate the ability to create confined 3D spin textures and topological defects by locally interfacing geometries of opposite chirality. The ability to create chiral spin textures via 3D nanopatterning alone enables exquisite control over the properties and location of complex topological magnetic states, of great importance for the development of future metamaterials and devices in which chirality provides enhanced functionality.

Half-hedgehog spin textures in sub-100 nm soft magnetic nanodots.

Topologically non-trivial structures such as magnetic skyrmions are nanometric spin textures of outstanding potential for spintronic applications due to their unique features. It is well known that Néel skyrmions of definite chirality are stabilized by the Dzyaloshinskii-Moriya exchange interaction (DMI) in bulk non-centrosymmetric materials or ultrathin films with strong spin-orbit coupling at the interface. In this work, we show that soft magnetic (permalloy) hemispherical nanodots are able to host three-dimensional chiral structures (half-hedgehog spin textures) with non-zero tropological charge. They are observed at room temperature, in absence of DMI interaction and they can be further stabilized by the magnetic field arising from the Magnetic Force Microscopy probe. Micromagnetic simulations corroborate the experimental data. Our work implies the existence of a new degree of freedom to create and manipulate complex 3D spin-textures in soft magnetic nanodots and opens up future possibilities to explore their magnetization dynamics.

Tunable resistivity exponents in the metallic phase of epitaxial nickelates.

We report a detailed analysis of the electrical resistivity exponent of thin films of NdNiO3 as a function of epitaxial strain. Thin films under low strain conditions show a linear dependence of the resistivity versus temperature, consistent with a classical Fermi gas ruled by electron-phonon interactions. In addition, the apparent temperature exponent, n, can be tuned with the epitaxial strain between n = 1 and n = 3. We discuss the critical role played by quenched random disorder in the value of n. Our work shows that the assignment of Fermi/Non-Fermi liquid behaviour based on experimentally obtained resistivity exponents requires an in-depth analysis of the degree of disorder in the material.

Observation of unexpected uniaxial magnetic anisotropy in La2/3Sr1/3MnO3 films by a BaTiO3 overlayer in an artificial multiferroic bilayer.

We studied in detail the in-plane magnetic properties of heterostructures based on a ferroelectric BaTiO3 overlayer deposited on a ferromagnetic La2/3Sr1/3MnO3 film grown epitaxially on pseudocubic (001)-oriented SrTiO3, (LaAlO3)0.3(Sr2TaAlO6)0.7 and LaAlO3 substrates. In this configuration, the combination of both functional perovskites constitutes an artificial multiferroic system with potential applications in spintronic devices based on the magnetoelectric effect. La2/3Sr1/3MnO3 single layers and BaTiO3/La2/3Sr1/3MnO3 bilayers using the pulsed-laser deposition technique. We analyzed the films structurally through X-ray reciprocal space maps and high-angle annular dark field microscopy, and magnetically via thermal demagnetization curves and in-plane magnetization versus applied magnetic field loops at room temperature. Our results indicate that the BaTiO3 layer induces an additional strain in the La2/3Sr1/3MnO3 layers close to their common interface. The presence of BaTiO3 on the surface of tensile-strained La2/3Sr1/3MnO3 films transforms the in-plane biaxial magnetic anisotropy present in the single layer into an in-plane uniaxial magnetic anisotropy. Our experimental evidence suggests that this change in the magnetic anisotropy only occurs in tensile-strained La2/3Sr1/3MnO3 film and is favored by an additional strain on the La2/3Sr1/3MnO3 layer promoted by the BaTiO3 film. These findings reveal an additional mechanism that alters the magnetic behavior of the ferromagnetic layer, and consequently, deserves further in-depth research to determine how it can modify the magnetoelectric coupling of this hybrid multiferroic system.

Customized MFM probes based on magnetic nanorods.

Focused Electron Beam Induced Deposition (FEBID) for magnetic tip fabrication is presented in this work as an alternative to conventional sputtering-based Magnetic Force Microscopy (MFM) tips. FEBID enables the growth of a high-aspect-ratio magnetic nanorod with customized geometry and composition to overcome the key technical limitations of MFM probes currently on the market. The biggest advantage of these tips, in comparison with CoCr coated pyramidal probes, lies in the capability of creating sharp ends, nearly 10 nm in diameter, which provides remarkable (topographic and magnetic) lateral resolution in samples with magnetic features close to the resolution limits of the MFM technique itself. The shape of the nanorods produces a very confined magnetic stray field, whose interaction with the sample is extremely localized and perpendicular to the surface, with negligible in-plane components. This effect can lead to a better analytical and numerical modelling of the MFM probes and to an increase in the sensitivity without perturbing the magnetic configuration of soft samples. Besides, the high-aspect ratio achievable in FEBID nanorod tips makes them magnetically harder than the commercial ones, reaching coercive fields higher than 900 Oe. According to the results shown, tips based on magnetic nanorods grown by FEBID can be eventually used for quantitative analysis in MFM measurements. Moreover, the customized growth of Co- or Fe-based tips onto levers with different mechanical properties allows MFM studies that demand different measuring conditions. To showcase the versatility of this type of probe, as a last step, MFM is performed in a liquid environment, which still remains a challenge for the MFM community largely due to the lack of appropriate probes on the market. This opens up new possibilities in the investigation of magnetic biological samples.

High Volume-Per-Dose and Low Resistivity of Cobalt Nanowires Grown by Ga+ Focused Ion Beam Induced Deposition.

The growth of ferromagnetic nanostructures by means of focused-Ga+-beam-induced deposition (Ga+-FIBID) using the Co2(CO)8 precursor has been systematically investigated. The work aimed to obtain growth conditions allowing for the simultaneous occurrence of high growth speed, good lateral resolution, low electrical resistivity, and ferromagnetic behavior. As a first result, it has been found that the competition between deposition and milling that is produced by the Ga+ beam is a limiting factor. In our working conditions, with the maximum available precursor flux, the maximum deposit thickness has been found to be 65 nm. The obtained volumetric growth rate is at least 50 times higher than in the case of deposition by focused-electron-beam-induced deposition. The lateral resolution of the deposits can be as good as 50 nm while using Ga+-beam currents lower than 10 pA. The high metallic content of the as-grown deposits gives rise to a low electrical resistivity, within the range 20-40 µΩ·cm. Magnetic measurements confirm the ferromagnetic nature of the deposits at room temperature. In conclusion, the set of obtained results indicates that the growth of functional ferromagnetic nanostructures by Ga+-FIBID while using the Co2(CO)8 precursor is a viable and competitive technique when compared to related nanofabrication techniques.

Diameter modulation of 3D nanostructures in focused electron beam induced deposition using local electric fields and beam defocus.

Focused electron beam induced deposition (FEBID) is a leading nanolithography technique in terms of resolution and the capability for three-dimensional (3D) growth of functional nanostructures. However, FEBID still presents some limitations with respect to the precise control of the dimensions of the grown nano-objects as well as its use on insulating substrates. In the present work, we overcome both limitations by employing electrically-biased metal structures patterned on the surface of insulating substrates. Such patterned metal structures serve for charge dissipation and also allow the application of spatially-dependent electric fields. We demonstrate that such electric fields can dramatically change the dimensions of the growing 3D nanostructures by acting on the primary electron beam and the generated secondary electrons. In the performed experiments, the diameter of Pt-C and W-C vertical nanowires grown on quartz, MgO and amorphous SiO2 is tuned by application of moderate voltages (up to 200 V) on the patterned metal microstructures during growth, achieving diameters as small as 50 nm. We identify two competing effects arising from the generated electric fields: a slight change in the primary beam focus point and a strong action on the secondary electrons. Beam defocus is exploited to achieve the in situ modulation of the diameter of 3D FEBID structures during growth.

Double-walled iron oxide nanotubes via selective chemical etching and Kirkendall process.

Double-walled oxide nanotube structures are interesting for a wide range of applications, from photocatalysis to drug delivery. In this work, a progressive oxidation method to fabricate double-walled nanotube structures is reported in detail. The approach is based on the electrodeposition of metallic iron nanowires, in porous alumina templates, followed by a selective chemical etching, nanoscale Kirkendall effect, a fast oxidation and out-diffusion of the metallic core structure during thermal annealing. To validate the formation mechanism of such core-shell structure, chemical composition and atomic structure were assessed. The resulting hematite nanotubes have a high degree of uniformity, along several microns, and a nanoscopic double-walled structure.

Magnetic Shape Memory Turns to Nano: Microstructure Controlled Actuation of Free-Standing Nanodisks.

Magnetic shape memory materials hold a great promise for next-generation actuation devices and systems for energy conversion, thanks to the intimate coupling between structure and magnetism in their martensitic phase. Here novel magnetic shape memory free-standing nanodisks are proposed, proving that the lack of the substrate constrains enables the exploitation of new microstructure-controlled actuation mechanisms by the combined application of different stimuli-i.e., temperature and magnetic field. The results show that a reversible areal strain (up to 5.5%) can be achieved and tuned in intensity and sign (i.e., areal contraction or expansion) by the application of a magnetic field. The mechanisms at the basis of the actuation are investigated by experiments performed at different length scales and directly visualized by several electron microscopy techniques, including electron holography, showing that thermo/magnetomechanical properties can be optimized by engineering the martensitic microstructure through epitaxial growth and lateral confinement. These findings represent a step forward toward the development of a new class of temperature-field controlled nanoactuators and smart nanomaterials.

Direct and converse piezoelectric responses at the nanoscale from epitaxial BiFeO3 thin films grown by polymer assisted deposition.

We use an original water-based chemical method to grow pure epitaxial BiFeO3 (BFO) ultra-thin films with excellent piezoelectric properties. Particularly, we show that this novel chemical route produces higher natural ferroelectric domain size distribution and coercive field compared to similar BFO films grown by physical methods. Moreover, we measured the d33 piezoelectric coefficient of 60 nm thick BFO films by a direct approach, using Direct Piezoelectric Force Microscopy (DPFM). As a result, first piezo-generated charge maps of a very thin BFO layer were obtained applying this novel technology. We also performed a comparative study of the d33 coefficients between standard PFM analysis and DPFM microscopy showing similar values i.e. 17 pm V-1 and 22 pC N-1, respectively. Finally, we proved that the directionality of the piezoelectric effect in BFO ferroelectric thin films is preserved at low thickness dimensions demonstrating the potential of chemical processes for the development of low cost functional ferroelectric and piezoelectric devices.