Spinodal decomposition introduces strain-enhanced thermochromism in polycrystalline V1-xTixO2 thin films.

Processes of self-organization play a key role in the development of innovative functional nanocomposites, allowing, in particular, the transformation of metastable solid solutions into multilayers by activating spinodal decomposition instead of layer-by-layer film growth. We report the formation of strained layered (V,Ti)O2 nanocomposites in thin polycrystalline films using a spinodal decomposition. Already during the growth of V0.65Ti0.35O2 films, spinodal decomposition was detected while producing atomic-scale disordered V- and Ti-rich phases. Post-growth annealing enhances compositional modulation, arranges the local atomic structures of the phases, and yields periodically layered nanostructures that resemble superlattices. The coherent interfacing of the V- and Ti-rich layers results in the compression of the V-rich phase along the c-axis of the rutile structure and enables strain-enhanced thermochromism. The latter is characterized by a simultaneous decrease in the temperature and width of the metal-insulator transition in the V-rich phase. Our results provide proof-of-concept for an alternative strategy to develop VO2-based thermochromic coatings by introducing strain-enhanced thermochromism into polycrystalline thin films.

Thermal Transport Evolution Due to Nanostructural Transformations in Ga-Doped Indium-Tin-Oxide Thin Films.

We report on a comprehensive theoretical and experimental investigation of thermal conductivity in indium-tin-oxide (ITO) thin films with various Ga concentrations (0-30 at. %) deposited by spray pyrolysis technique. X-ray diffraction (XRD) and scanning electron microscopy have shown a structural transformation in the range 15-20 at. % Ga from the nanocrystalline to the amorphous phase. Room temperature femtosecond time domain thermoreflectance measurements showed nonlinear decrease of thermal conductivity in the range 2.0-0.5 Wm-1 K-1 depending on Ga doping level. It was found from a comparison between density functional theory calculations and XRD data that Ga atoms substitute In atoms in the ITO nanocrystals retaining Ia-3 space group symmetry. The calculated phonon dispersion relations revealed that Ga doping leads to the appearance of hybridized metal atom vibrations with avoided-crossing behavior. These hybridized vibrations possess shortened mean free paths and are the main reason behind the thermal conductivity drop in nanocrystalline phase. An evolution from propagative to diffusive phonon thermal transport in ITO:Ga with 15-20 at. % of Ga was established. The suppressed thermal conductivity of ITO:Ga thin films deposited by spray pyrolysis may be crucial for their thermoelectric applications.