Self-assembly of oxides as a bottom-up approach to functional nanostructures goes beyond the conventional nanostructure formation based on lithographic techniques. Particularly, chemical solution deposition (CSD) is an ex situ growth approach very promising for high throughput nanofabrication at low cost. Whereas strain engineering as a strategy to define nanostructures with tight control of size, shape and orientation has been widely used in metals and semiconductors, it has been rarely explored in the emergent field of functional complex oxides. Here we will show that thermodynamic modeling can be very useful to understand the principles controlling the growth of oxide nanostructures by CSD, and some attractive kinetic features will also be presented. The methodology of strain engineering is applied in a high degree of detail to form different sorts of nanostructures (nanodots, nanowires) of the oxide CeO2 with fluorite structure which then is used as a model system to identify the principles controlling self-assembly and self-organization in CSD grown oxides. We also present, more briefly, the application of these ideas to other oxides such as manganites or BaZrO3. We will show that the nucleation and growth steps are essentially understood and manipulated while the kinetic phenomena underlying the evolution of the self-organized networks are still less widely explored, even if very appealing effects have been already observed. Overall, our investigation based on a CSD approach has opened a new strategy towards a general use of self-assembly and self-organization which can now be widely spread to many functional oxide materials.
We have investigated the mechanisms of epitaxial development and functional properties of oxide thin films (Ce 0.9 Zr 0.1 O 2-y , LaNiO 3 and Ba 0.8 Sr 0.2 TiO 3) grown on single crystal substrates (Y 2 O 3 :ZrO 2 , LaAlO 3 and SrTiO 3) by the chemical solution deposition approach. Rapid thermal annealing furnaces are very powerful tools in this study providing valuable information of the early stages of nucleation, the kinetics of epitaxial film growth and the coarsening of nanocrystalline phases. Advanced transmission electron microscopies, x-ray diffraction and atomic force microscopy are employed to investigate the film microstructure and morphology, microstrain relaxation and epitaxial crystallization. We demonstrate that the isothermal evolution towards epitaxial film growth follows a self-limited process driven by atomic diffusion, and surface and interface energy minimization. All investigated oxides
Highly crystalline epitaxial Ba0.8Sr0.2TiO3 (BST) thin-films are grown on (001)-oriented LaNiO3-buffered LaAlO3 substrates by pulsed laser irradiation of solution derived barium-zirconium-titanium precursor layers using a UV Nd:YAG laser source at atmospheric conditions. The structural analyses of the obtained films, studied by X-ray diffractometry and transmission electron microscopy, demonstrate that laser processing allows the growth of tens of nm-thick BST epitaxial films with crystalline structure similar to that of films obtained through conventional thermal annealing methods. However, the fast pulsed nature of the laser employed leads to crystallization kinetic evolution orders of magnitude faster than in thermal treatments. The combination of specific photothermal and photochemical mechanisms is the main responsible for the ultrafast epitaxial laser-induced crystallization. Piezoresponse microscopy measurements demonstrate equivalent ferroelectric behavior in laser and thermally annealed films, being the piezoelectric constant ∼25 pm V−1.
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