Multi-wavelength Raman scattering of nanostructured Al-doped zinc oxide

In this work we present a detailed Raman scattering investigation of zinc oxide and aluminum-doped zinc oxide (AZO) films characterized by a variety of nanoscale structure and morphology and synthesized by pulsed laser deposition (PLD) under different oxygen pressure conditions. The comparison of Raman data for pure ZnO and AZO films with similar morphology at the nano/mesoscale allows to investigate the relation between Raman features (peak or band positions, width, relative intensity) and material properties such as local structural order, stoichiometry and doping. Moreover Raman measurements with three different excitation lines (532, 457 and 325 nm) point out a strong correlation between vibrational and electronic properties. This observation confirms the relevance of a multi-wavelength Raman investigation to obtain a complete structural characterization of advanced doped oxide materials.

Hierarchically organized nanostructured TiO2 for photocatalysis applications

A template-free process for the synthesis of nanocrystalline TiO2 hierarchical microstructures by reactive Pulsed Laser Deposition (PLD) is here presented. By a proper choice of deposition parameters a fine control over the morphology of TiO2 microstructures is demonstrated, going from classical compact/columnar films to a dense forest of distinct hierarchical assemblies of ultrafine nanoparticles (<10 nm), up to a more disordered, aerogel-type structure. Correspondingly, film density varies with respect to bulk TiO2 anatase, with a degree of porosity going from 48% to over 90%. These structures are stable with respect to heat treatment at 400 centigrade degrees, which results in crystalline ordering but not in morphological changes down to the nanoscale. Both as deposited and annealed films exhibit very promising photocatalytic properties, even superior to standard Degussa P25 powder, as demonstrated by the degradation of stearic acid as a model molecule. The observed kinetics are correlated to the peculiar morphology of the PLD grown material. We show that the 3D multi-scale hierarchical morphology enhances reaction kinetics and creates an ideal environment for mass transport and photon absorption, maximizing the surface area-to-volume ratio while at the same time providing readily accessible porosity through the large inter-tree spaces that act as distributing channels. The reported strategy provides a versatile technique to fabricate high aspect ratio 3D titania microstuctures through a hierarchical assembly of ultrafine nanoparticles. Beyond photocatalytic and catalytic applications, this kind of material could be of interest for those applications where high surface-to-volume and efficient mass transport are required at the same time.