New Mechanism for Long Photo-Induced Enhanced Raman Spectroscopy in Au Nanoparticles Embedded in TiO2.

The photo-induced enhanced Raman spectroscopy (PIERS) effect is a phenomenon taking place when plasmonic nanoparticles deposited on a semiconductor are illuminated by UV light prior to Raman measurement. Results from the literature show that the PIERS effect lasts for about an hour. The proposed mechanism for this effect is the creation of oxygen vacancies in the semiconductor that would create a path for charge transfer between the analyte and the nanoparticles. However, this hypothesis has never been confirmed experimentally. Furthermore, the tested structure of the PIERS substrate has always been composed of plasmonic nanoparticles deposited on top of the semiconductor. Here, gold nanoparticles co-deposited with porous TiO2 are used as a PIERS substrate. The deposition process confers the nanoparticles a unique position half buried in the nanoporous semiconductor. The resulting PIERS intensity is among the highest measured until now but most importantly the duration of the effect is significantly longer (at least 8 days). Cathodoluminescence measurements on these samples show that two distinct mechanisms are at stake for co-deposited and drop-casted gold nanoparticles. The oxygen vacancies hypothesis tends to be confirmed for the latter, but the narrowing of the depletion zone explains the long PIERS effect.

Highly sensitive detection of estradiol by a SERS sensor based on TiO2 covered with gold nanoparticles.

We propose the use of gold nanoparticles grown on the surface of nanoporous TiO2 films as surface-enhanced Raman scattering (SERS) sensors for the detection of 17ß-estradiol. Gold deposition on top of a TiO2 surface leads to the formation of nanoparticles the plasmonic properties of which fulfil the requirements of a SERS sensor. The morphological and optical properties of the surface were investigated. Specifically, we demonstrate that the TiO2 background pressure during pulsed laser deposition and the annealing conditions offer control over the formation of Au nanoparticles with different sizes, shapes and distributions, yielding a versatile sensor. We have exploited the surface for the detection of 17ß-estradiol, an emerging contaminant in environmental waters. We have found a limit of detection of 1 nM with a sensitivity allowing for a dynamic range of five orders of magnitude (up to 100 µM).