Crystalline organic semiconducting thin films from the benchmark molecule C8-BTBT-C8 were obtained using physical vapor deposition and various solution-based methods. Utilizing atomic force microscopy and X-ray spectromicroscopy, we illustrate the influence of the underlying growth mechanism and determine the highly preparation-dependent orientation of the thiophene backbone. We observe a continuous trend for crystalline C8-BTBT-C8 thin film domains to extend into the square millimeter-range under near-equilibrium growth conditions. For such well-defined systems, electron diffraction tomography allows us to precisely determine the unit cell directly after film deposition and to reveal an 8°molecular tilt angle with respect to the surface normal. This finding is in almost perfect accordance with the values derived from near-edge X-ray absorption fine structure linear dichroism. Within this work, we shine a light on both the successes and challenges connected to the realization of potent, thiophene-based semiconducting films, paving the way toward square centimeter-sized ultrathin organic crystals and their application in organic circuitry.
The molecular self-organization of alkyl-functionalized hexathiophene monolayers prepared at the solvent-water interface is investigated by complementary microscopy techniques. Our study focuses on the influence of solvents and initial droplet volume...
Two-dimensionally (2D) extended thin films of p-type organic semiconductor C 13 -BTBT (BTBT = [1]benzothieno[3,2-b]-[1]benzothiophene) were fabricated via self-controlled growth at the liquid−liquid interface. Depicting a compound class originally developed for further functionalization and subsequent realization of self-assembled monolayers (SAMs), the potent BTBT core unit commonly excels in high-quality structure formation as well as charge-transport characteristics. Utilizing a manifold spectromicroscopic toolbox, we observe extraordinarily crystalline C 13 -BTBT films with an upright standing configuration of the backbone unit accounting for superior intermolecular orbital overlap. The well-defined morphology and internal structure of the film are being underpinned by charge-transport parameters that are in the range of comparable organic electronic devices based on bisubstituted BTBT films from the same processing technique. The inherently favorable membrane-like bilayer molecular arrangement is confirmed by unambiguous representation of the unit cell as derived from electron tomography.
We present an in operando near-edge x-ray absorption fine structure (NEXAFS) study on p-type [11-(benzo[b]benzo[4,5]thieno[2,3-d]thiophen-2-yl)dodecyl)] BTBT-based self-assembled monolayer (BTBT-SAM) films. As a 2D-model system, the BTBT-SAM offers direct insight into the active organic semiconductor layer without interfering bulk materials. This allows for the observation of polaronic states caused by charged species at the dielectric/organic interface. Linear NEXAFS dichroism is employed to derive the molecular orientation of the BTBT subunit. Field-induced modifications in the unoccupied molecular orbitals are observed in the NEXAFS spectra. The spectral changes in the on- and off-states are discussed in the context of polaron formation due to charge accumulation induced by the applied electric field.
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