▎ 摘　　要

We present a systematic study in investigating the orientation characteristics of pentacene molecules grown on graphene substrates using polarized Raman spectroscopy. The substrate-induced orientation alignment of pentacene can be well distinguished through the polarized Raman spectra. Interestingly, we found that the nature of polycrystalline graphene not only provides efficient route to control molecular orientation, but also acts as an excellent template allowing conjugated molecules to stack accordingly. The relative orientation of the well-aligned pentacene molecules and the nearby graphene domains exhibits several preferred angles due to atomic interactions. This unique feature is further examined and verified by single domain graphene. Furthermore, polarized Raman spectroscopy contains abundant information allowing us to analyze the ordering level of pentacene films with various thicknesses, which provides insightful perspectives of manipulating molecular orientations with graphene and spatial organization between conjugated systems, in a more quantitative manner.