Thermomechanical Behavior of Poly(3-hexylthiophene) Thin Films on the Water Surface

The thermomechanical behavior of a conjugated polymer (CP) in a thin film state has rarely been studied despite the importance of understanding the polymer morphologies and optimizing the thermal processes of organic semiconductors. Moreover, the seamless integration of multilayers without mechanical failures in CP-based electronic devices is crucial for determining their operational stability. Large differences in the coefficients of thermal expansion (CTEs) between the multilayers can cause serious degradation of devices under thermal stress. In this study, we measure the intrinsic thermomechanical properties of poly(3-hexylthiophene) (P3HT) thin films in a pseudo-freestanding state on the water surface. The as-cast P3HT thin films exhibited a large thermal shrinkage (-1001 ppm K^-1) during heating on the water surface. Morphological analyses revealed that the thermal shrinkage of the polymer films was caused by the rearrangement of the polymer chain networks accompanied by crystallization, thus indicating that preheating the polymer films is essential for estimating their intrinsic CTE values. Moreover, the rigidity of the substrate significantly influences the thermomechanical behavior of the polymer films. The polymer films that were preheated on the glass substrate showed nonlinear thermal expansion due to the substrate constraint inhibiting sufficient relaxation of the polymer chains. In comparison, a linear expansion behavior is observed after preheating the films on the water surface, exhibiting a consistent CTE value (185 ppm K^-1) regardless of the number of thermal strain measurements. Thus, this work provides a direct method for measuring in-plane CTE values and an in-depth understanding of the thermomechanical behaviors of CP thin films to design thermomechanically reliable organic semiconductors.