Optimized grafting density of end-functionalized polymers to polar dielectric surfaces for solution-processed organic field-effect transistors.

Polystyrene (PS) grafted to silicon oxide (SiO2, referred to as gPS-SiO2) bilayers generated via a polymer grafting method were used as organic-oxide hybrid gate dielectrics to fabricate solution-processed triethylsilylethynyl anthradithiophene (TES-ADT) organic field-effect transistors (OFETs). The dielectric surface properties were significantly altered by the areal grafting densities of different molecular weight (Mw) PS chains with end-functionalized dimethylchlorosilane attached to the SiO2 surfaces. Lesser grafting densities of longer PS chains increased the surface roughness of the treated SiO2 surfaces from 0.2 to 1.5 nm, as well as the water contact angles from 94° to 88°. Below a critical Mw of end-functionalized PS, the gPS chains on the SiO2 surfaces appeared to form a brush-like conformation with an areal density value greater than 0.1 chains nm(-2), but other high-Mw gPS chains formed pancake structures in which the polymeric layers were easily incorporated with solution-processed TES-ADT as a solute. These findings indicate that low-density gPS layers interfered with the self-assembly of TES-ADT in cast films, causing great decreases in crystal grain size and π-conjugated orientation. The presence of compact gPS chains on the SiO2 surface could yield high electrical performance of TES-ADT OFETs with a field-effect mobility of 2.1 cm2 V(-1) s(-1), threshold voltage of -2.0 V, and on/off current ratio of greater than 10(7) when compared to those developed using less-concentrated gPS-SiO2 surfaces.