Study of titania nanorod films deposited by matrix-assisted pulsed laser evaporation as a function of laser fluence

Chemically synthesized brookite titanium dioxide (TiO2) nanorods with average diameter and length dimensions of 3–4 nm and 35–50 nm, respectively, were deposited by the matrix-assisted pulsed laser evaporation technique. A toluene nanorod solution was frozen at the liquid-nitrogen temperature and irradiated with a KrF excimer laser (λ=248 nm, τ=20 ns) at the repetition rate of 10 Hz, at different fluences (25 to 350 mJ/cm2). The deposited films were structurally characterized by high-resolution scanning and transmission electron microscopy. 〈100〉 single-crystal Si wafers and carbon-coated Cu grids were used as substrates. Structural analyses evidenced the occurrence of brookite-phase crystalline nanospheres coexisting with individually distinguishable TiO2 nanorods in the films deposited at fluences varying from 50 to 350 mJ/cm2. Nanostructured TiO2 films comprising only nanorods were deposited by lowering the laser fluence to 25 mJ/cm2. The observed shape and phase transitions of the nanorods are discussed taking into account the laser-induced heating effects, reduced melting temperature and size-dependent thermodynamic stability of nanoscale TiO2.