Thickness Dependence of Doping Level in Conducting Polymer Films: the Optical Contrast Optimization in Electrochromism as a Case Study

Comprehensive Summary Doping plays an essential role in the properties of conducting polymers. Film thickness not only has a direct influence on their photoelectric properties, but also affects the doping ability, which may lead to the decline of capacitance and electrochromic properties caused by incomplete doping. Therefore, it is essential to study the quantitative relationship between doping level and film thickness in application. Herein, empirical formula between doping level and thickness was obtained by studying the spectroelectrochemistry behaviors of two different electrochromic materials, poly( N , N '‐bis(3,5‐(2‐thienyl)‐phenyl)‐1,6,7,12‐tetrachloroperylene‐3,4,9,10‐perylenetetracarboxylic diimide) (poly(Th‐Cl‐PBI)) and poly(3,4‐ethylenedioxythiophene) (PEDOT). The doping level is verified to be correlated to the reciprocal of the 3 rd power of film thickness. Experimental results fit these formulas very well, giving correlation coefficient R 2 higher than 0.99. The optical contrast prediction of these two electrochromic materials is also used to verify this relationship formula. For the first time, we quantitatively connect these two important parameters of conducting polymers, doping level and thickness.