Nanostructured Surfaces Frustrate Polymer Semiconductor Molecular Orientation


Johnston, D.E.; Yager, K.G.; Hlaing, H.; Lu, X.; Ocko, B.M.; Black, C.T. "Nanostructured Surfaces Frustrate Polymer Semiconductor Molecular Orientation" ACS Nano 2014, 8 243–249.
doi: 10.1021/nn4060539


Grazing-incidence x-ray scattering is used to probe the orientation of a semiconducting polymer confined into nanoscale gratings. We find that nanoconfinement frustrates the usual interface-directed ordering.


Nanostructured grating surfaces with groove widths less than 200 nm impose boundary conditions that frustrate the natural molecular orientational ordering within thin films of blended polymer semiconductor poly(3-hexlythiophene) and phenyl-C61-butyric acid methyl ester, as revealed by grazing incidence X-ray scattering measurements. Polymer interactions with the grating sidewall strongly inhibit the polymer lamellar alignment parallel to the substrate typically found in planar films, in favor of alignment perpendicular to this orientation, resulting in a preferred equilibrium molecular configuration difficult to achieve by other means. Grating surfaces reduce the relative population of the parallel orientation from 30% to less than 5% in a 400 nm thick film. Analysis of in-plane X-ray scattering with respect to grating orientation shows polymer backbones highly oriented to within 10 degrees of parallel to the groove direction.