Graphene
and semiconducting polymers have been extensively researched
for use in many microelectronic devices. For both devices with layered
structures and graphene–semiconducting polymer composite materials,
molecular interactions between graphene and semiconducting polymers
play significant roles in determining the interfacial properties and
impact the device performance. In this research, molecular orientations
of polymer backbones of three polythiophenes (PTs) with different
side-chain lengths at the buried PT/graphene interfaces were determined
using sum frequency generation (SFG) vibrational spectroscopy. It
was found that the longer the PT side chain, the larger the PT backbone
tilt angle measured. Therefore, the PT backbone with a longer side-chain
length adopts a more lying-down pose on graphene. The same trend for
orientation tilt angles of PTs with different side-chain lengths at
PT/CaF2 interfaces was observed. When comparing the same
PT backbone orientation, PT at the PT/graphene interface generally
lies down more compared to that at the PT/CaF2 interface,
due to stronger π–π interactions between the PT
backbone conjugated rings and graphene. The different PT backbone
orientations at interfaces are likely caused by varied interactions
between the PT backbone and the substrate and between side chains
and the substrate, as well as intermolecular and intramolecular interactions
between PT molecules (including side chains and backbones). The determination
of PT backbone orientations at buried interfaces helps to understand
molecular interactions at these interfaces, aiding in the design of
polymer/graphene interfaces with optimal structure and improved properties.