Molecular ordering in monolayers of an alkyl-Substituted perylene-bisimide dye by attenuated total reflectance ultraviolet-visible spectroscopy

Surface-relative orientational parameters were determined for monolayer films of N, N'-ditridecylperylenetetracarboxylic dianhydridediimide (C ₁₃-PTCDI) in terms of the relative electronic transition dipole strengths, providing a three-dimensional view of the absorption dipole distribution. In order to obtain a macroscopically ordered film, C ₁₃-PTCDI was deposited by (1) horizontal Langmuir-Blodgett (LB) transfer onto methyl- and phenyl-silanized glass, and (2) vapor deposition onto oriented films of poly(tetrafluoroethylene) (PTFE) on glass. Films of LB-deposited C ₁₃-PTCDI were found to be completely Isotropic prior to annealing. After annealing, these films remained isotropic in the plane of the substrate while the out-of-plane anisotropy was significantly enhanced. In contrast, films of C ₁₃-PTCDI vapor deposited onto oriented poly(tetrafluoroethylene) (PTFE)-modified substrates yielded films with a high degree of both in- and out-of-plane anisotropy. Atomic force microscopy (AFM) images of both the LB- and vapor-deposited films show substantial differences in film morphology and long-range order. These results demonstrate that molecular orientation in C ₁₃-PTCDI films can be controlled by varying substrate surface chemistry and post-deposition processing.