Critical role of alkyl chain branching of organic semiconductors in enabling solution-processed N-channel organic thin-film transistors with mobility of up to 3.50 cm² V(-1) s(-1).

Substituted side chains are fundamental units in solution processable organic semiconductors in order to achieve a balance of close intermolecular stacking, high crystallinity, and good compatibility with different wet techniques. Based on four air-stable solution-processed naphthalene diimides fused with 2-(1,3-dithiol-2-ylidene)malononitrile groups (NDI-DTYM2) that bear branched alkyl chains with varied side-chain length and different branching position, we have carried out systematic studies on the relationship between film microstructure and charge transport in their organic thin-film transistors (OTFTs). In particular synchrotron measurements (grazing incidence X-ray diffraction and near-edge X-ray absorption fine structure) are combined with device optimization studies to probe the interplay between molecular structure, molecular packing, and OTFT mobility.

Observation of a distinct surface molecular orientation in films of a high mobility conjugated polymer.

The molecular orientation and microstructure of films of the high-mobility semiconducting polymer poly(N,N-bis-2-octyldodecylnaphthalene-1,4,5,8-bis-dicarboximide-2,6-diyl-alt-5,5-2,2-bithiophene) (P(NDI2OD-T2)) are probed using a combination of grazing-incidence wide-angle X-ray scattering (GIWAXS) and near-edge X-ray absorption fine-structure (NEXAFS) spectroscopy. In particular a novel approach is used whereby the bulk molecular orientation and surface molecular orientation are simultaneously measured on the same sample using NEXAFS spectroscopy in an angle-resolved transmission experiment. Furthermore, the acquisition of bulk-sensitive NEXAFS data enables a direct comparison of the information provided by GIWAXS and NEXAFS.

Microstructure of polycrystalline PBTTT films: domain mapping and structure formation.

We utilize near-edge X-ray absorption fine structure (NEXAFS) spectroscopy and scanning transmission X-ray microscopy (STXM) to study the microstructure and domain structure of polycrystalline films of the semiconducting polymer poly(2,5-bis(3-tetradecylthiophen-2-yl)thieno[3,2-b]thiophene) (PBTTT). Total electron yield NEXAFS spectroscopy is used to examine the surface structure of the first 1-2 molecular layers, while bulk-sensitive STXM is used to produce maps of domain orientation and order sampled through the entire film thickness. We study different phases of PBTTT including as-cast, terraced and nanoribbon morphologies produced via spin-coating as well as aligned films of as-cast and nanoribbon morphologies produced by zone-casting.

Observation of a type II heterojunction in a highly ordered polymer-carbon nanotube nanohybrid structure.

We report a study of the electronic properties of the heterojunction between regioregular poly(3-hexylthiophene) (rrP3HT) and single-walled carbon nanotubes (SWNTs). Comparison of the spectroscopic data of nanotube dispersions in a range of polymers indicates significant changes in the nature of the observed SWNT excitons only in combination with rrP3HT. A detailed analysis concludes that a type II heterojunction between rrP3HT and small diameter s-SWNTs is formed, making these particular nanohybrids a promising material for organic photovoltaics.