Directionally oriented LB films of an OPE derivative: assembly, characterization, and electrical properties.
ABSTRACT Langmuir films have been fabricated from 4-[4'-(4''-thioacetyl-phenyleneethynylene)-phenyleneethynylene]-aniline (NOPES) after cleavage of the thioacetyl protecting group. Characterization by surface pressure vs area per molecule isotherms and Brewster angle microscopy reveal the formation of a high quality monolayer at the air-water interface. One layer Langmuir-Blodgett (LB) films were readily fabricated by the transfer of the NOPES Langmuir film onto solid substrates. X-ray photoelectron spectroscopy (XPS), surface polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS), and quartz crystal microbalance (QCM) experiments conclusively demonstrate the formation of one layer LB films in which the functional group associated with binding to the substrate can be tailored by the film transfer conditions. Using LB methods this molecule could be transferred to gold samples with either the amine or thiol group attached to the gold surface. The amine group is directly attached to the gold substrate (Au-NH(2)-OPE-SH) when the substrate is initially immersed in the subphase and withdrawn during the transfer process; in contrast, monomolecular films in which the thiolate group is attached to the gold substrate (Au-S-OPE-NH(2)) are obtained when the substrate is initially out of the subphase and immersed during the transfer process. The morphology of these films was analyzed by atomic force microscopy (AFM), showing the formation of homogeneous layers. Film homogeneity was confirmed by cyclic voltammetry, which revealed a large passivation of gold electrodes covered by NOPES monolayers. Electrical properties for both polar orientated junctions have been investigated by scanning tunnelling microscopy (STM), with both orientations featuring a nonrectifying behavior.