Sub‐Band Filling and Hole Transport in Polythiophene‐Based Electrolyte‐Gated Transistors: Effect of Side‐Chain Length and Density.

The relationship between hole density and conductivity in electrochemically gated polythiophene films is examined. The films are integrated into electrolyte‐gated transistors (EGTs), so that hole accumulations can be electrochemically modulated up to ≈0.4 holes per thiophene ring (hpr). Polythiophenes include poly(3‐alkylthiophenes) (P3ATs) with four different side chain lengths – butyl (P3BT), hexyl (P3HT), octyl (P3OT), or decyl (P3DT) – and poly[2,5‐bis(3‐dodecylthiophen‐2‐yl)thieno[3,2‐b]thiophene] (PBTTT) and poly(3,3′′′‐didodecyl[2,2′:5′,2′′:5′′,2′′′‐quaterthiophene]‐5,5′′′‐diyl) (PQT). Analysis of the drain current – gate voltage (ID–VG) and gate current – gate voltage (IG–VG) characteristics of the EGTs reveals that all six polythiophene semiconductors exhibited reversible conductivity peaks at 0.12 – 0.15 hpr. Conductivity is suppressed beyond ≈0.4 hpr.The maximum carrier mobilities of the P3AT semiconductors increase, and hysteresis of the conductivity peaks decreases, with increasing alkyl side‐chain length. PBTTT and PQT with reduced side chain densities exhibit the largest hysteresis but have higher hole mobilities. The results suggest that at ≈0.4 hpr, a polaronic sub‐band is filled in all cases. Filling of the sub‐band correlates with a collapse in the hole mobility. The side‐chain dependence of the peak conductivity and hysteresis further suggests that Coulombic ion‐carrier interactions are important in these systems. Tailoring ion‐carrier correlations is likely important for further improvements in transport properties of electrochemically doped polythiophenes. [ABSTRACT FROM AUTHOR]