Defect engineering operated on metal oxides by chemical and structural modifications may strongly affect properties suitable for various applications such as photoelectrochemical behaviour, charge transport and luminescence. In this work we report the tuneable optical features observed in undoped monoclinic HfO 2 nanocrystals and their dependence on the structural properties of the material at the nanoscale. Transmission electron microscopy together with X-ray diffraction and surface area measurements were used to determine the fine structural modifications, in terms of crystal growth and coalescence of crystalline domains, occurring during a calcination process in the temperature range from 400 to 1000 °C. The fit of the broad optical emission into spectral components, together with time resolved photoluminescence, allowed us to identify the dual nature of the emission at 2.5 eV, where an ultrafast defect-related intrinsic luminescence (with decay time of few ns) overlaps with a slower emission (decay of several µs) due to extrinsic Ti -impurity centres. Moreover, the evolution of intrinsic visible bands during the material transformation was monitored. The relationship between structural parameters uniquely occurring in nanosized materials and the optical properties was investigated and tentatively modelled. The blue emissions at 2.5 and 2.9 eV are clearly related to defects lying at crystal boundaries, while an unprecedented emission at 2.1 eV enables, at relatively low calcination temperatures, the white luminescence of HfO 2 under near-UV excitation.
We present the assembly of preformed antimony doped tin oxide nanobuilding blocks into centimeter sized aerogels with surface areas exceeding 340 m(2) g(-1). After calcination, the resistivity of the aerogels was decreased by 4 orders of magnitude to a few kΩ cm, with the primary conducting structures measuring only a few nanometers.
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