Evaluation of Sputtering Processes in Strontium Iridate Thin Films.

The growth of epitaxial thin films from the Ruddlesden-Popper series of strontium iridates by magnetron sputtering is analyzed. It was found that, even using a non-stoichiometric target, the films formed under various conditions were consistently of the perovskite-like n = ∞ SrIrO3 phase, with no evidence of other RP series phases. A detailed inspection of the temperature-oxygen phase diagram underscored that kinetics mechanisms prevail over thermodynamics considerations. The analysis of the angular distribution of sputtered iridium and strontium species indicated clearly different spatial distribution patterns. Additionally, significant backsputtering was detected at elevated temperatures. Thus, it is assumed that the interplay between these two kinetic phenomena is at the origin of the preferential nucleation of the SrIrO3 phase. In addition, strategies for controlling cation stoichiometry off-axis have also been explored. Finally, the long-term stability of the films has been demonstrated.

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.

X-ray Absorption Spectroscopy Study of Thickness Effects on the Structural and Magnetic Properties of Pr2-δNi1-xMn1+xO6-y Double Perovskite Thin Films.

In this work, we report a systematic study of the influence of film thickness on the structural and magnetic properties of epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite grown on top of two different (001)-SrTiO3 and (001)-LaAlO3 substrates by RF magnetron sputtering. A strong dependence of the structural and magnetic properties on the film thickness is found. The ferromagnetic transition temperature (TC) and saturation magnetization (Ms) are found to decrease when reducing the film thickness. In our case, the thinnest films show a loss of ferromagnetism at the film-substrate interface. In addition, the electronic structure of some characteristic PNMO samples is deeply analyzed using X-ray absorption spectroscopy (XAS) and X-ray magnetic circular dichroism (XMCD) measurements and compared with theoretical simulations. Our results show that the oxidation states of Ni and Mn ions are stabilized as Ni2+ and Mn4+, thus the ferromagnetism is mainly due to Ni2+-O-Mn4+ superexchange interactions, even in samples with poor ferromagnetic properties. XMCD results also make evident large variations on the spin and orbital contributions to the magnetic moment as the film's thickness decreases.

Optimization of the Growth Process of Double Perovskite Pr2-δNi1-xMn1+xO6-y Epitaxial Thin Films by RF Sputtering.

Epitaxial thin films of Pr2-δNi1-xMn1+xO6-y (PNMO) double perovskite were grown on (001)-oriented SrTiO3 substrates by RF magnetron sputtering. The influence of the growth parameters (oxygen pressure, substrate temperature, and annealing treatments) on the structural, magnetic and transport properties, and stoichiometry of the films was thoroughly investigated. It is found that high-quality epitaxial, insulating, and ferromagnetic PNMO thin films can only be obtained in a narrow deposition parameter window. It is shown that a careful selection of the growth conditions allows for obtaining a high degree of Ni/Mn cation ordering, which is reflected in the values of the Curie temperature, TC, and saturation magnetization, MS, which are very close to those of bulk material.

Formation of Nickel Oxide Nanocuboids in Ferromagnetic La2Ni1-xMn1+xO6.

The control of the spontaneous formation of nanostructures at the surface of thin films is of strong interest in many different fields, from catalysts to microelectronics, because surface and interfacial properties may be substantially enhanced. Here, we analyze the formation of nickel oxide nanocuboids on top of La2Ni1-xMn1+xO6 double perovskite ferromagnetic thin films, epitaxially grown on SrTiO3 (001) substrates by radio-frequency (RF) magnetron sputtering. We show that, by annealing the films at high temperature under high oxygen partial pressure, the spontaneous segregation of nanocuboids is enhanced. The evolution of the structural and magnetic properties of the films is studied as a function of the annealing treatments at different temperatures. It is shown that the formation of NiOx nanocuboids leads to a nanostructured film surface with regions of locally different electrical transport characteristics.

Spontaneous in-flight assembly of magnetic nanoparticles into macroscopic chains.

Knowing the interactions controlling aggregation processes in magnetic nanoparticles is of strong interest in preventing or promoting nanoparticles' aggregation at wish for different applications. Dipolar magnetic interactions, proportional to the particle volume, are identified as the key driving force behind the formation of macroscopic aggregates for particle sizes above about 20 nm. However, aggregates' shape and size are also strongly influenced by topological ordering. 1-D macroscopic chains of several micrometer lengths are obtained with cube-shaped magnetic nanoparticles prepared by the gas-aggregation technique. Using an analytical model and molecular dynamics simulations, the energy landscape of interacting cube-shaped magnetic nanoparticles is analysed revealing unintuitive dependence of the force acting on particles with the displacement and explaining pathways leading to their assembly into long linear chains. The mechanical behaviour and magnetic structure of the chains are studied by a combination of atomic and magnetic force measurements, and computer simulation. The results demonstrate that [111] magnetic anisotropy of the cube-shaped nanoparticles strongly influences chain assembly features.

Nanoscale mechanical control of surface electrical properties of manganite films with magnetic nanoparticles.

Mechanical control of electrical properties in complex heterostructures, consisting of magnetic FeO x nanoparticles on top of manganite films, is achieved using atomic force microscope (AFM) based methods. Under applied pressure of the AFM tip, drop of the electrical conductivity is observed inducing an electrically insulating state upon a critical normal load. Current and surface potential maps suggest that the switching process is mainly governed by the flexoelectric field induced at the sample surface. The relaxation process of the electrical surface potential indicates that the diffusion of oxygen vacancies from the bulk of the manganite films towards the sample surface is the dominant relaxation mechanism. The magnetic FeO x nanoparticles, staying attached to the sample surface after the rubbing, protect the underlying manganite films and provide stability of the observed resistive switching effect. The employed mechanical control gives a new freedom in the design of resistive switching devices since it does not depend on the film thickness, and biasing is not needed.

Self-Arranged Misfit Dislocation Network Formation upon Strain Release in La0.7Sr0.3MnO3/LaAlO3(100) Epitaxial Films under Compressive Strain.

Lattice-mismatched epitaxial films of La0.7Sr0.3MnO3 (LSMO) on LaAlO3 (001) substrates develop a crossed pattern of misfit dislocations above a critical thickness of 2.5 nm. Upon film thickness increases, the dislocation density progressively increases, and the dislocation spacing distribution becomes narrower. At a film thickness of 7.0 nm, the misfit dislocation density is close to the saturation for full relaxation. The misfit dislocation arrangement produces a 2D lateral periodic structure modulation (Λ ≈ 16 nm) alternating two differentiated phases: one phase fully coherent with the substrate and a fully relaxed phase. This modulation is confined to the interface region between film and substrate. This phase separation is clearly identified by X-ray diffraction and further proven in the macroscopic resistivity measurements as a combination of two transition temperatures (with low and high Tc). Films thicker than 7.0 nm show progressive relaxation, and their macroscopic resistivity becomes similar than that of the bulk material. Therefore, this study identifies the growth conditions and thickness ranges that facilitate the formation of laterally modulated nanocomposites with functional properties notably different from those of fully coherent or fully relaxed material.

Macroscopic evidence of nanoscale resistive switching in La2/3Sr1/3MnO3 micro-fabricated bridges.

In this work we report on a combined macro, micro and nanoscale investigation where electronic transport properties through La⅔Sr⅓MnO3 (LSMO) microfabricated bridges, in which nano-sized resistive states are induced by using a conducting scanning probe microscope (C-SPM), are analyzed. The strategy intentionally avoids the standard capacitor-like geometry, thus allowing the study of the electronic transport properties of the locally modified region, and approaches the integration of functional oxides in low dimensional devices while providing macroscopic evidence of nanoscale resistive switching (RS). The metallic and ferromagnetic LSMO is locally modified from its low resistance state (LRS) to a high resistance state (HRS) when a bias voltage is applied on its surface through the conducting tip, which acts as a mobile electrode. Starting from a metallic oxide the electroforming process is not required, thus avoiding one of the major drawbacks for the implementation of memory devices based on RS phenomena. The application of a bias voltage generates an electric field that promotes charge depletion, leading to a strong increase of the resistance, i.e. to the HRS. This effect is not only confined to the outermost surface layer, its spatial extension and final HRS condition can be modulated by the magnitude and duration of the potential applied, opening the door to the implementation of multilevel devices. In addition, the half-metallic character, i.e. total spin polarization, of LSMO might allow the implementation of memory elements and active spintronic devices in the very same material. The stability of the HRS and LRS as a function of temperature, magnetic field and compliance current is also analyzed, allowing the characterization of the nature of the switching process and the active material.

Competing misfit relaxation mechanisms in epitaxial correlated oxides.

Strain engineering of functional properties in epitaxial thin films of strongly correlated oxides exhibiting octahedral-framework structures is hindered by the lack of adequate misfit relaxation models. Here we present unreported experimental evidence of a four-stage hierarchical development of octahedral-framework perturbations resulting from a progressive imbalance between electronic, elastic, and octahedral tilting energies in La(0.7)Sr(0.3)MnO(3) epitaxial thin films grown on SrTiO(3) substrates. Electronic softening of the Mn-O bonds near the substrate leads to the formation of an interfacial layer clamped to the substrate with strongly degraded magnetotransport properties, i.e., the so-called dead layer, while rigid octahedral tilts become relevant at advanced growth stages without significant effects on charge transport and magnetic ordering.

Controlling exchange bias in Co-CoOx nanoparticles by oxygen content.

We report on the occurrence of exchange bias on laser-ablated granular thin films composed of Co nanoparticles embedded in an amorphous zirconia matrix. The deposition method allows one to control the degree of oxidation of the Co particles by tuning the oxygen pressure at the vacuum chamber (from 2 x 10(-5) to 10(-1) mbar). The nature of the nanoparticles embedded in the nonmagnetic matrix is monitored from metallic, ferromagnetic (FM) Co to antiferromagnetic (AFM) CoO(x), with a FM/AFM intermediate regime for which the percentage of the AFM phase can be increased at the expense of the FM phase, leading to the occurrence of exchange bias in particles of about 2 nm in size. For an oxygen pressure of about 10(-3) mbar the ratio between the FM and AFM phases is optimum with an exchange bias field of about 900 Oe at 1.8 K. The mutual exchange coupling between the AFM and FM is also at the origin of the induced exchange anisotropy on the FM leading to high irreversible hysteresis loops, and the blocking of the AFM clusters due to proximity to the FM phase.

Strain-driven self-assembled network of antidots in complex oxide thin films.

Structural strain due to lattice mismatch is used to promote the formation of a self-assembled network of antidots in highly epitaxial La(2/3)Sr(1/3)MnO(3) thin films grown on (001) oriented SrTiO(3) substrates by radiofrequency magnetron sputtering. Size, depth, and separation between antidots can be controlled by changing deposition parameters and the miscut angle of the substrate. This morphology exhibits a remarkable magnetic anisotropy and offers unique opportunities for versatile nanostencils for the preparation of nano-object networks that can be of major relevance for the fabrication of oxide-based magnetic and magnetoelectronic devices.

Particle growth mechanisms in Ag-ZrO(2) and Au-ZrO(2) granular films obtained by pulsed laser deposition.

Thin films consisting of Ag and Au nanoparticles embedded in amorphous ZrO(2) matrix were grown by pulsed laser deposition in a wide range of metal volume concentrations in the dielectric regime (0.08