Electrochemical and structural characterization of nanocomposite Agy:TiNx thin films for dry bioelectrodes: the effect of the N/Ti ratio and Ag content

By P. Pedrosa and D. Machado and P. Fiedler and E. Alves and N.P. Barradas and J. Haueisen and F. Vaz and C. Fonseca
Published in Electrochimica Acta NULL 2015

Abstract

\ABSTRACT\ Agy:TiNx nanocomposite thin films sputtered with different N/Ti atomic ratios and Ag atomic contents were characterized from the structural and morphological points of view. Their electrochemical behaviour was studied in a synthetic sweat solution, aiming at selecting a suitable material for biolectrode applications. An increase of the N/Ti atomic ratio, which is accompanied by an increase of the Ag atomic content, leads to a substantial increase of the roughness and porosity of the samples, especially for N/Ti ratios >0.2. For N/Ti atomic ratios up to 0.3 (15 at.% Ag) no metallic Ag segregation is visible in the TiNx matrix. Hence, the possible formation of TiAg and Ti2Ag intermetallics or even a Ag/TiAg/Ti2Ag phase mixture, although not demonstrated, should not be disregarded. As for the N/Ti atomic ratio = 0.7 (32 at.% Ag) sample, the Ag phases are predominantly concentrated near the interface with the substrate. The amount of Ag phases at the surface of the films remains somewhat low for all TiN under-stoichiometric films, even for Ag atomic contents up to 32 at.%. When the TiNx matrix reaches the stoichiometric condition (sample with N/Ti atomic ratio = 1 and 20 at.% Ag), Ag segregation occurs and metallic Ag aggregates are visible at the surface of the film, leading to a substantially different electrochemical behaviour. The impedance of the Agy:TiNx films in synthetic sweat solution is mainly ruled by the roughness/porosity variation, thus the higher the N/Ti atomic ratio, the lower the impedance. The interfacial film/sweat electrochemical noise and drift were similar for all films and comparable to the results obtained for commercial Ag/AgCl electrodes (except for the N/Ti atomic ratio = 1 and 20 at.% Ag film). In view of the results, it may be concluded that the samples with N/Ti atomic ratios = 0.3 (15 at.% Ag) and 0.7 (32 at.% Ag) are the most appropriate for further bioelectrode development.

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