In this work, the sensor response of MPcF_x (M = Cu, Co, Zn; x = 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_x 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, MPcF₁₆ 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%).

In this work, thin films of vanadyl phthalocyanines (VOPc and VOPcF₄) are studied as active layers for the detection of gaseous ammonia and hydrogen. The effect of F-substituents on the structural features of vanadyl phthalocyanine films and their sensor response toward ammonia (10–50 ppm) and hydrogen (100–500 ppm) is investigated by X-ray diffraction (XRD) and chemiresistive methods, respectively. It is shown that the sensor response of VOPcF₄ films to ammonia is 2–3 times higher than that of VOPc films. By contrast, the sensor response to hydrogen is higher in the case of VOPc films. Apart from this, the hybrid structures of vanadyl phthalocyanine films with Pd nanoparticles deposited on their surface by a chemical vapor deposition method are also tested to reveal the effect of Pd nanoparticles on the sensitivity of VOPc films to hydrogen. Deposition of Pd nanoparticles on the surface of VOPc films leads to the noticeable increase of their sensitivity to hydrogen.