The growth mechanism and polymer density in conjugated polymer brush (CPB) films composed of poly(3-methylthiophene) (P3MT) are characterized. X-ray photoelectron spectroscopy experiments show that the initiation of aryl halide monolayers by Pd(PtBu3)2 produces disproportionated monolayer initiators. Unlike disproportionated species formed during the solution-phase initiation of aryl halides, which cannot mediate polymerization, the surface-bound initiators catalyze polymerization to form CPB films with a high grafting density (1.2 nm-2). Rutherford backscattering spectrometry (RBS) experiments show that P3MT CPB films have a characteristic monomer volume density (3.7 nm-3) that is indistinguishable from the volume density of spuncast poly(3-hexylthiophene) films. Using these RBS and XPS results, characteristics of P3MT CPB growth are obtained, including the turnover frequency (7.5 h-1) and polymer molecular weight (300 g/mol·nm)
