José Manuel Vila-Fungueiriño

Room-Temperature Ferromagnetism in Thin Films of LaMnO3 Deposited by a Chemical Method Over Large Areas

Hole-doping into the Mott insulator LaMnO3 results in a very rich magneto-electric phase diagram, including colossal magnetoresistance and different types of charge and orbital ordering. On the other hand, LaMnO3 presents an important catalytic activity for oxygen reduction, which is fundamental for increasing the efficiency of solid-oxide fuel cells and other energy-conversion devices. In this work, we report the chemical solution (water-based) synthesis of high-quality epitaxial thin films of LaMnO3, free of defects at square-centimeter scales, and compatible with standard microfabrication techniques. The films show a robust ferromagnetic moment and large magnetoresistance at room temperature. Through a comparison with films grown by pulsed laser deposition, we show that the quasi-equilibrium growth conditions characteristic of this chemical process can be exploited to tune new functionalities of the material.

High quality thin films of thermoelectric misfit cobalt oxides prepared by a chemical solution method

Misfit cobaltates ([Bi/Ba/Sr/Ca/CoO]nRS[CoO2]q) constitute the most promising family of thermoelectric oxides for high temperature energy harvesting. However, their complex structure and chemical composition makes extremely challenging their deposition by high-vacuum physical techniques. Therefore, many of them have not been prepared as thin films until now. Here we report the synthesis of high-quality epitaxial thin films of the most representative members of this family of compounds by a water-based chemical solution deposition method. The films show an exceptional crystalline quality, with an electrical conductivity and thermopower comparable to single crystals. These properties are linked to the epitaxial matching of the rock-salt layers of the structure to the substrate, producing clean interfaces free of amorphous phases. This is an important step forward for the integration of these materials with complementary n-type thermoelectric oxides in multilayer nanostructures.

Tunnel Conduction in Epitaxial Bilayers of Ferromagnetic LaCoO3/La2/3Sr1/3MnO3 Deposited by a Chemical Solution Method

We report magnetic and electronic transport measurements across epitaxial bilayers of ferromagnetic insulator LaCoO3 and half-metallic ferromagnet La2/3Sr1/3MnO3 (LCO/LSMO: 3.5 nm/20 nm) fabricated by a chemical solution method. The I-V curves at room temperature and 4K measured with conducting atomic force microscopy (CAFM) on well-defined patterned areas exhibit the typical features of a tunneling process. The curves have been fitted to the Simmons model to determine the height (φ) and width (s) of the insulating LCO barrier. The results yield φ = 0.40 ± 0.05 eV (0.50 ± 0.01 eV) at room temperature (4K) and s = 3 nm, in good agreement with the structural analysis. Our results demonstrate that this chemical method is able to produce epitaxial heterostructures with the quality required for this type of fundamental studies and applications.

Thermodynamic conditions during growth determine the magnetic anisotropy in epitaxial thin-films of La0.7Sr0.3MnO3

The suitability of a particular material for use in magnetic devices is determined by the process of magnetization reversal/relaxation, which in turn depends on the magnetic anisotropy. Therefore, designing new ways to control magnetic anisotropy in technologically important materials is highly desirable. Here we show that magnetic anisotropy of epitaxial thin-films of half-metallic ferromagnet La0.7Sr0.3MnO3 (LSMO) is determined by the proximity to thermodynamic equilibrium conditions during growth. We performed a series of x-ray diffraction and ferromagnetic resonance (FMR) experiments in two different sets of samples: the first corresponds to LSMO thin-films deposited under tensile strain on (0 0 1) SrTiO3 by pulsed laser deposition (PLD; far from thermodynamic equilibrium); the second were deposited by a slow chemical solution deposition (CSD) method, under quasi-equilibrium conditions. Thin films prepared by PLD show fourfold in-plane magnetic anisotropy, with an overimposed uniaxial term. However, the uniaxial anisotropy is completely suppressed in the CSD films. This change is due to a different rotation pattern of MnO6 octahedra to accommodate epitaxial strain, which depends not only on the amplitude of tensile stress imposed by the STO substrate, but also on the growth conditions. Our results demonstrate that the nature and magnitude of the magnetic anisotropy in LSMO can be tuned by the thermodynamic parameters during thin-film deposition.

Integration of functional complex oxide nanomaterials on silicon

The combination of standard wafer-scale semiconductor processing with the properties of functional oxides opens up to innovative and more efficient devices with high value applications that can be produced at large scale. This review uncovers the main strategies that are successfully used to monolithically integrate functional complex oxide thin films and nanostructures on silicon: the chemical solution deposition approach (CSD) and the advanced physical vapor deposition techniques such as oxide molecular beam epitaxy (MBE). Special emphasis will be placed on complex oxide nanostructures epitaxially grown on silicon using the combination of CSD and MBE. Several examples will be exposed, with a particular stress on the control of interfaces and crystallization mechanisms on epitaxial perovskite oxide thin films, nanostructured quartz thin films, and octahedral molecular sieve nanowires. This review enlightens on the potential of complex oxide nanostructures and the combination of both chemical and physical elaboration techniques for novel oxide-based integrated devices.

Polymer assisted deposition of epitaxial oxide thin films

Chemical solution methods for thin-film deposition constitute an affordable alternative to high-vacuum physical technologies, like Sputtering, Pulsed Laser Deposition (PLD) or Molecular Beam Epitaxy (MBE). Particularly, chemical methods have proven to be very suitable for producing functional films over large areas, especially in the relatively thick range, from >100 nm to microns. Also, their versatile ability to synthesize different types of materials, i.e. carbides, silicides, pnictides, oxides or chalcogenides, makes them very attractive for a wide range of applications and studies. However, problems with surface/interface roughness, control of stoichiometry in multicationic or precisely-doped materials, and a lack of accurate control of the thickness in the thin limit range (<20 nm) has reduced the competitiveness of these processes over high vacuum physical methods. This is particularly true in the case of multicationic oxide thin-films, which have experienced frantic research activity in recent years associated with phenomena of interactions across atomically sharp interfaces; the vast majority of oxide thin films used in these studies were deposited under high vacuum. Here, we review the Polymer Assisted Deposition (PAD) of epitaxial thin-films, with particular emphasis on the case of oxides. As we will show in this review, PAD is very versatile for producing different structural phases (perovskites, spinels, garnets, etc.), demonstrating its competitiveness in producing oxide thin-films with the quality required for fundamental studies and applications, as well as its complementarity to physical methods for stabilizing metastable materials and composite heterostructures. We also provide a detailed step by step description of the most relevant chemical aspects of the method, in order to make it reproducible and attractive to laboratories with little experience in complex chemistry tasks.

Epitaxial La0.7Sr0.3MnO3 thin films on silicon with excellent magnetic and electric properties by combining physical and chemical methods

ABSTRACT Half-metallic ferromagnetic La0.7Sr0.3MnO3 (LSMO) represents an appealing candidate to be integrated on silicon substrates for technological devices such as sensors, data storage media, IR detectors, and so on. Here, we report high-quality epitaxial LSMO thin films obtained by an original combination of chemical solution deposition (CSD) and molecular beam epitaxy (MBE). A detailed study of the thermal, chemical, and physical compatibility between SrTiO3 (STO)/Si buffer layers and LSMO films, grown by MBE and CSD, respectively, enables a perfect integration of both materials. Importantly, we show a precise control of the coercive field of LSMO films by tuning the mosaicity of the STO/Si buffer layer. These results demonstrate the enormous potential of combining physical and chemical processes for the development of low-cost functional oxide-based devices compatible with the complementary metal oxide semiconductor technology. Graphical Abstract