Tuning Molecular Conformations to Enhance Spontaneous Orientation Polarization in Organic Thin Films

Three isomeric derivatives of 2,2',2″-(1,3,5-benzinetriyl)-tris(1-phenyl-1-H-benzimidazole) (TPBi) bearing ethyl groups on the N-phenyl moieties were synthesized to elucidate the effects of intramolecular interactions on spontaneous orientation polarization (SOP) in thin films. The films of the TPBi derivatives displayed enhanced SOP with a surface potential change of up to 1.8 times that for TPBi, and the p-substituted derivative exhibited the largest potential change reported to date (+141.0 mV/nm). Density functional theory calculations and single-crystal structure analysis suggest that the introduction of the ethyl groups switched the stable molecular conformation from C₁ to C₃ symmetry. Through analysis of the structural anisotropy in the films by spectral ellipsometry and two-dimensional (2D) grazing-incidence wide-angle X-ray scattering, we conclude that the conformational change of the molecules was the major factor underlying the SOP enhancement.