Growth and Characterization of Films Containing Fullerenes and Water Soluble Porphyrins for Solar Energy Conversion Applications

Thin films consisting of two fulleropyrrolidine derivatives 1 or 2 and a water-soluble porphyrin, TPPS4, were prepared by the Langmuir−Schäfer (LS, horizontal lifting) method. In particular, a solution of the fulleropyrrolidine in chloroform and dimethyl sulfoxide was spread on the water surface, while the porphyrin (bearing peripheral anionic sulfonic groups) was dissolved into the aqueous subphase. To the best of our knowledge, such a versatile method for film fabrication of fullerene/porphyrin mixed composite films has never been used by other researchers. Evidence of the effective interactions between the two components at the air−water interface was obtained from the analysis of the floating layers by means of surface pressure vs area per molecule Langmuir curves, Brewster angle microscopy, and UV−visible reflection spectroscopy. The characterization of the LS films by UV−visible spectroscopy reveals that in each case the two constituents behave as strongly interacting π systems. The use of polarized light suggests the existence of a preferential direction of the TPPS4 macrocyclic rings with an edge-on arrangement with respect to the substrate surface, regardless which fulleropyrrolidine derivative is in the composite film. Atomic force microscopy investigations give evidence of morphologically flat layers even for LS transfer at low surface pressures. Photoaction spectra were recorded from films deposited by only one horizontal lifting onto indium−tin−oxide (ITO) electrodes, and the observed photocurrent increased notably with increasing transfer surface pressure for both 1/TPPS4 and 2/TPPS4 composite films. IPCE values are larger for 2/TPPS4 systems in comparison with 1/TPPS4 composite layers. Finally, a nonconventional approach to photoinduced phenomena is proposed by differential spectroscopy in the FT−IR attenuated total reflectance (ATR) mode.