Molecular Dynamics Insights into Substrate-Induced Gradient Stiffness and Vibrational Modes in P3AT Thin Films

In this study, we reveal the emergence of a tri-regime gradient in stiffness across substrate-supported poly(3-alkylthiophene) (P3AT) thin films, comprising an adsorbed region, a bulk-like region, and a free surface region. The stiffness distribution is found to be largely independent of the degree of polymerization but is significantly modulated by side chain length and temperature. Specifically, longer side chains (bead count = 4) expand the adsorbed and free surface regions, while elevating temperature above the glass transition leads to an order-of-magnitude reduction in stiffness. Phonon mode analysis demonstrates a clear inverse correlation between vibrational frequency and both the degree of polymerization and temperature, with side chain length exerting minimal influence. A high phonon mode similarity index between the main and side chains indicates coupled vibrational dynamics. Interfacial energy decomposition confirms that van der Waals interactions, particularly through distinct π–π stacking, dominate the substrate adhesion. These findings provide fundamental insights into the nanoscale thermomechanical properties of P3AT thin films on silica substrates, offering valuable guidance for the interface engineering of P3AT-on-silica systems in organic electronics.