There is a critical need to develop a method to pattern semiconducting polymers for device applications on the sub-micrometer scale.

Doping-induced solubility control (DISC) patterning is a recently developed technique that uses the change in polymer solubility upon doping, along with an optical dedoping process, to achieve high-resolution optical patterning. DISC patterning can produce features smaller than predicted by the diffraction limit; however, no mechanism has been proposed to explain such high resolution. Here, we use diffraction to spatially modulate the light intensity and determine the dissolution rate, revealing a superlinear dependence on light intensity. This rate law is independent of wavelength, indicating that patterning resolution is not dominated by an optical dedoping reaction, as was previously proposed. Instead we show here that the optical patterning mechanism is primarily controlled by the thermal profile generated by the laser. To quantify this effect, the thermal profile and dissolution rate are modeled using a finite-element model and compared against patterned line cross sections as a function of wavelength, laser intensity, and dwell time. Our model reveals that although the laser-generated thermal profile is broadened considerably beyond the profile of the laser, the highly temperature dependent dissolution rate results in selective dissolution near the peak of the thermal profile. Therefore, the key factor in achieving super-resolution patterning is a strongly temperature dependent dissolution rate, a common feature of many polymers. In addition to suggesting several routes to improved resolution, our model also demonstrates that doping is not required for optical patterning of conjugated polymers, as was previously believed. Instead, we demonstrate that superlinear resolution optical patterning should be attainable in any conjugated polymer simply by tuning the solvent quality during patterning, thus extending the applicability of our method to a wide class of materials. We demonstrate the generality of photothermal patterning by writing sub-400 nm features into undoped PffBT4T-2OD.