Substituent effects on packing entropy and film morphologies in the nucleation of functionalized pentacenes on SiO(2) substrate: Molecular dynamics simulations

The changes in structural ordering, packing entropy, free energy, and film morphologies in the initial nucleation processes of pentacene (Pn), 6, 13-bis(t-butylethynyl) pentacene (t-Bu Pn), and 6, 13-bis(triisopropylsilylethynyl) pentacene (TIPS Pn) on the SiO(2) substrate were investigated, by using the molecular dynamics simulations. During the nucleation, the rod-like Pn molecules tend to diffuse rapidly and have different orientations on the SiO(2) surface. At the low coverage, the t-Bu Pn and TIPS Pn molecules with the branched topological structures almost lie flat on the substrate. On the basis of statistical distribution of various packing configurations of the functionalized Pn pairs, the packing entropy is estimated according to the Boltzmann formula. The packing entropy abruptly decreases in the early stage of deposition. Once the critical nucleus size is reached, the packing entropy converges to a constant value. As the coverage increases, the monolayer films of Pn and its branched derivatives become more ordered. The TIPS Pn with the relatively larger molecular area would occasionally stand on the surface during the nucleation, resulting in the dramatic changes in free energy. In the monolayers, the functionalized Pn molecules are packing more orderly than those in amorphous solids, but less orderly than those in crystals. The degree of order of these monolayers increases as the size of the substituents increases. The understanding of substituent effects on nucleation processes and packing structures is helpful to fabricate organic thin films with well-predefined molecular orientations.