Local Orientation of Polystyrene at the Interface with Poly(methyl methacrylate) in Block Copolymer.

The local conformation of polystyrene (PS) at the phase-separated lamellar interface with poly(methyl methacrylate) (PMMA) in their diblock copolymer (BCP) was examined by sum-frequency generation spectroscopy in conjunction with a full-atomistic molecular dynamics simulation. While PS phenyl groups of BCP were oriented in the interfacial region, they were random in the bulk. Such an interfacial orientation of phenyl groups was not clear for the corresponding blend of PS and PMMA. The PS backbone of BCP was in-plane oriented and folded near to the chemical junction point located in the interfacial region and the orientation became random at several nanometers distant. No evidence for the chain folding at the interface was found for the blend system.