Discrimination of mercuric ions in piezoelectric sensors with a conjugated polymeric active layer

The synthetic conjugated poly(1,4-arylene-2,5-thienylene) containing benzo[c][2,1,3]thiadiazole monomeric units (Bz-PAT) is proposed as active layer for the selective detection of mercuric ions. The Bz-PAT polymer chemical structure induces the formation of a disordered film with numerous vacancies and the size of these defects could be exploited for a reversible trapping of mercuric ions. For these reasons the Langmuir-Schaefer (LS) deposition method has been employed for transferring Bz-PAT layers with the desired accurate bi-dimensional organization control of the layer and with a high control of the deposition parameters. In this contribution, the frequency variation of quartz crystal microbalances functionalized with 10, 20, 30 and 40 LS runs of Bz-PAT have been investigated in response to the injection of aqueous solutions of HgCl2, Pb(NO3)2, NiCl2, CdCl2 and ZnSO4 at different concentrations (0.5 mM, 1 mM, 5 mM). An almost linear dependence on the number of the LS layers and hence on the film thickness, measured by means of ellipsometric spectroscopy, has been found in terms of sensor response to concentration of Hg2+ ions fluxed. By means of UV-Vis spectroscopy, the variations in the π-π* absorption band of the polymer, attributed to the thiophene segment, induced by HgCl2 injection has been analyzed and explained as a consequence of the electron transfer from the mercuric ion to the polymer solid film. These results, together with the linear relation found between the number of deposited layers and LS film thickness, suggest that the sensing mechanism can be explained both by an electron interaction between active layer and analyte and a diffusion mechanism of Hg2+ into the solid film that reaches an asymptotic value at 30 runs (about 80 nm), then a higher number of layers does not influence the sensor sensibility.