Organic semiconductors (OSCs) offer a new avenue to the next-generation electronics, but the lack of a scalable and inexpensive nanoscale patterning/deposition technique still limits their use in electronic applications. Recently, a new lithographic etching technique has been introduced that uses molecular dopants to reduce semiconducting polymer solubility in solvents and a direct-write laser to remove dopants locally, enabling rapid OSC etching with diffraction limited resolution. Previous publications postulated that the reaction that enables patterning is a photochemical reaction between photoexcited dopants with neutral solvent molecules. In this work, we analyze the photoinduced dissolution kinetics of F4TCNQ doped P3HT films using time-resolved in situ optical probing. We find two competing mechanisms that control de-doping and dissolution: the first is the photochemical reaction posited in the literature, and the second involves direct heating of the polymer by the laser, inducing increased solubility for both the polymer and dopant. We show that the wavelength-specific photochemical effect is dominant in low photon doses while the photothermal effect is dominant with high excitation rates regardless of laser wavelength. With sufficiently high optical intensity input, the photothermal mechanism can in principle achieve a high writing speed up to 1 m/s. Our findings bring new insights into the mechanisms behind laser direct writing of OSCs based on dopant induced solubility control and enable ultraprecise fabrications of various device configurations in large-scale manufacturing
