Nanolayers of selected porphyrin and phthalocyanine dyes on solid substrates studied by electronic absorption and IR reflection–absorption spectroscopy

Electronic absorption and IR reflection–absorption spectra in non-polarized and in polarized light for lead porphyrin as well as magnesium and lead phthalocyanine dyes when deposited in the form of Langmuir–Blodgett (LB) nanolayers on solid inorganic surfaces (quartz, semiconductor and metal) were measured. Some IR bands of the Langmuir–Blodgett dye layers’ spectra show frequency shifts and changes in the relative intensities as well as in half widths when compared with the vibrational features of powdered dyes dispersed in KBr pellets, which were used as references. The FT-IR spectroscopic examination of the Langmuir–Blodgett layers allowed to estimate electron redistribution at the interface between dye layer and solid substrates. The Langmuir–Blodgett films of different thicknesses (3, 5, 10 layers) were studied at various angles of IR beam incidence and different light polarizations. The most spectacular results were obtained for the grazing incidence (80°) and films of 5 layers for dyes on the Au substrate. The IR spectroscopy was supported with electronic absorption studies (UV–vis) to follow interaction at interface between the dye layers and the substrates as well as to evaluate linear dichroism and to determine arrangement of molecules in the Langmuir–Blodgett films. Molecular arrangement in the Langmuir–Blodgett layers was discussed. It was shown that the dye molecular planes are rather randomly oriented in the Langmuir–Blodgett films with a tendency that the Qy and Qx transition moments in the phthalocyanine macroring are slightly directed along the y-axis (Langmuir–Blodgett dipping direction) and the x-axis direction, respectively.