Combinatorial selectivity with an array of phthalocyanines functionalized TiO₂/ZnO heterojunction thin film sensors

The development of electronic noses requires the control of the selectivity pattern of each sensor of the array. Organic chemistry offers a manifold of possibilities to this regard but in many cases the chemical sensitivity is not matched with the response of electronic sensor. The combination of organic and inorganic materials is an approach to transfer the chemical sensitivities of the sensor to the measurable electronic signals. In this paper, this approach is demonstrated with a hybrid material made of phthalocyanines and a bilayer structure of ZnO and TiO₂. Results show that the whole spectrum of sensitivity of phthalocyanines results in changes of the resistance of the sensor, and even the adsorption of compounds, such as hexane, which cannot change the resistance of pure phthalocyanine layers, elicits changes of the sensor resistance. Furthermore, since phthalocyanines are optically active, the sensitivity in dark and visible light are different. Thus, operating the sensor in dark and light two different signals per sensors can be extracted. As a consequence, an array of 3 sensors made of different phthalocyanines results in a virtual array of six sensors. The sensor array shows a remarkable selectivity respect to a set of test compounds. Principal component analysis scores plot illustrates that hydrogen bond basicity and dispersion interaction are the dominant mechanisms of interaction.