P. Romero-Gómez, J. Toudert, J.R. Sánchez-Valencia, A. Borrás, A. Barranco, A.R. González-Elipe
Journal of Physical Chemistry C, 114 (2010) 20932–20940
doi: 10.1021/jp103902u

Nanoporous ZnO thin films presenting a tunable nanostructure and photoluminescence (PL) were grown by plasma enhanced vapor deposition on surface oxidized Si substrates. These films consist of c-axis oriented wurtzite ZnO nanocolumns whose topology, crystallinity, and PL can be tuned through the substrate temperature (varied in the 300−573 K range) and the nature of the plasma assistance (pure O₂, O₂/Ar, O₂/H₂, or O₂/N₂ mixture). In particular, these processing parameters influence the intensity of the UV and visible PL bands of the films, related to excitonic and defective radiative transitions, respectively. Increasing the substrate temperature enhances the UV PL and rubs out the visible PL due to the increase of grain size and the removal of interstitial defects. Additional tuning of the intensity ratio between the UV and visible bands can be done by controlling the film thickness. A decrease of the UV PL is observed when the films go thicker, an effect that is likely to be linked to the microstructure of the films rather than to their crystallinity that is improved upon increasing of the film thickness, as seen from PL spectroscopy and XRD measurements. Indeed, a gradient of stress, decreasing from the substrate to the surface, is evidenced and related to a concentration gradient of interstitial defects. The drawbacks of the thickness effect, which prohibits growing thick films with a high optical quality, can be bypassed by growing the films in a O₂/H₂ plasma.