Surface electronic properties of self-assembled, oppositely charged macrocycle and polymer multilayers on conductive oxides

Using the layer-by-layer self-assembly technique, we have deposited multilayer thin films on conductive indium tin oxide (ITO) surfaces by alternatively dipping ITO substrates in a polymer PDDA or poly(diallydimethylammonium) chloride solution and a macrocyle NiPc or nickel phthalocyanine solution. In addition to characterizing PDDA-NiPc systems with X-ray reflectometry and cyclic voltammetry, we monitored the growth of PDDA/NiPc multilayers on conductive oxides with Fourier transform infrared (IR) spectroscopy at an external grazing-angle reflection configuration. IR spectra with polarization perpendicular to the conductive ITO surfaces revealed vibration bands at 1227 and 1200 cm(-1) corresponding to salt bridges of -SO3-. . . Me2N+ = binding between PDDA and NiPc. An oscillation of the surface electronic potential was observed with a Kelvin Probe as the surface layer alternated between PDDA and NiPc. The average gap of the surface potential difference between NiPc and PDDA monolayers is about 400 mV. Oscillation of surface potential or work function is caused by the modulation in electron affinity of ITO due to the dipolar effect, generated by the highly charged layers of PDDA or NiPc.