Not Just Surface Energy: The Role of Bis(pentafluorophenoxy) Silicon Phthalocyanine Axial Functionalization and...

Understanding the effect of surface chemistry on the dielectric-semiconductor interface, thin-film morphology, and molecular alignment enables the optimization of organic thin-film transistors (OTFTs). We explored the properties of thin films of bis(pentafluorophenoxy) silicon phthalocyanine (F₁₀-SiPc) evaporated onto silicon dioxide (SiO₂) surfaces modified by self-assembled monolayers (SAMs) of varying surface energies and by weak epitaxy growth (WEG). The total surface energy (γ^tot), dispersive component of the total surface energy (γ^d), and polar component of the total surface energy (γ^p) were calculated using the Owens-Wendt method and related to electron field-effect mobility of devices (μ_e), and it was determined that minimizing γ^p and matching γ^tot yielded films with the largest relative domain sizes and highest resulting μ_e. Subsequent analyses were completed using atomic force microscopy (AFM) and grazing-incidence wide-angle X-ray scattering (GIWAXS) to relate surface chemistry to thin-film morphology and molecular order at the surface and semiconductor-dielectric interface, respectively. Films evaporated on n-octyltrichlorosilane (OTS) yielded devices with the highest average μ_e of 7.2 × 10^-2 cm²·V^-1·s^-1 that we attributed to it having both the largest domain length, which were extracted from power spectral density function (PSDF) analysis, and a subset of molecules with a pseudo edge-on orientation relative to the substrate. Films of F₁₀-SiPc with the mean molecular orientation of the π-stacking direction being more edge-on relative to the substrate also generally resulted in OTFTs with a lower average V_T. Unlike conventional MPcs, F₁₀-SiPc films fabricated by WEG experienced no macrocycle in an edge-on configuration. These results demonstrate the critical role of the F₁₀-SiPc axial groups on WEG, molecular orientation, and film morphology as a function of surface chemistry and the choice of SAMs.