Fluorinated Metal Phthalocyanines: Interplay between Fluorination Degree, Films Orientation, and Ammonia Sensing Properties

In this work, the sensor response of MPcF (M = Cu, Co, Zn; = 0, 4, 16) films toward gaseous NH₃ (10⁻50 ppm) was studied by a chemiresistive method and compared to that of unsubstituted MPc films to reveal the effects of central metals and F-substituents on the sensing properties. A combination of atomic force microscopy and X-ray diffraction techniques have been used to elucidate the structural features of thin MPcF films deposited by organic molecular beam deposition. It has been shown that the sensor response of MPcF₄ films to ammonia is noticeably higher than that of MPc films, which is in good correlation with the values of binding energy between the metal phthalocyanine and NH₃ molecules, as calculated by the density functional theory (DFT) method. At the same time, in contrast to the DFT calculations, MPcF demonstrated the lesser sensor response compared with MPcF₄, which appeared to be connected with the different structure and morphology of their films. The ZnPcF₄ films were shown to exhibit a sensitivity to ammonia up to concentrations as low as 0.1 ppm, and can be used for the selective detection of ammonia in the presence of some reducing gases and volatile organic compounds. Moreover, the ZnPcF₄ films can be used for the detection of NH₃ in the gas mixture simulating exhaled air (N₂ 76%, O₂ 16%, H₂O 5%, and CO₂ 3%).