Enhanced chemosensing of ammonia based on the novel molecular semiconductor-doped insulator (MSDI) heterojunctions

A series of new molecular semiconductor-doped insulator (MSDI) heterojunctions as conductimetric transducers to NH₃ sensing were fabricated based on a novel semiconducting molecular material, an amphiphilic tris(phthalocyaninato) rare earth triple-decker complex, Eu₂Pc(15C5)₄]₂Pc(OC₁₀H₂₁)₈], quasi-Langmuir-Shäfer (QLS) film, as a top-layer, and vacuum-deposited and cast film of CuPc as well as copper tetra-tert-butyl phthalocyanine (CuTTBPc) QLS film as a sub-layer, named as MSDIs 1, 2 and 3, respectively. MSDIs 1-3 and respective sub-layers prepared from three different methods were characterized by X-ray diffraction, electronic absorption spectra and current-voltage (I-V) measurements. Depending on the sub-layer film-forming method used, α-phase CuPc film structure, β-phase CuPc crystallites and H-type aggregates of CuTTBPc have been obtained, respectively. An increasing sensitivity to NH₃ at varied concentrations in the range of 15-800 ppm, follows the order MSDI 2 < MSDI 3 < MSDI 1, revealing the effect of sub-layer film structures on sensing performance of the MSDIs. In particular, the time-dependent current plot of the MSDI 1, with α-phase CuPc film as a sub-layer, clearly shows an excellent separation of the different ammonia concentration levels and nearly complete reversibility and reproducibility even at room temperature, which is unique among the phthalocyanine-based ammonia sensors thus far reported in the literature. This provides a general method to improve sensor response of organic heterojunctions by controlling and tuning the film structure of sub-layer with appropriate fabrication techniques. On the other hand, the enhanced sensitivity, stability and reproducible response of the MSDI 1 heterostructure in comparison with the respective single-layer films have also been obtained. A judicious combination of materials and molecular architectures has led to enhanced sensing properties of the MSDI 1, in which control at the molecular level can be achieved.