Here, we introduce the first experimental proof of coherent oscillation and coupling of photoswitchable molecules embedded randomly in a polymeric matrix and acting cooperatively upon illumination with UV light. In particular, we demonstrate the specular reflection and Brewster phenomenon alteration of photochromic molecular dipole antennas. We successfully demonstrate the concept of Brewster wavelength, which is based on the dipolar interaction between radiating dipoles and the surrounding matrix possessing a net dipole moment, as a key tool for highly localized sensing of matrix polarity. We also introduce the concept of 'tailored molecular photonic coupling' while highlighting the role of interferences for the design of optically active media by adjusting the photonic response of the medium with the real and imaginary refractive index of photoswitchable molecules in the 'ON' state. Our results enhance our fundamental understanding of coherent dipole radiation and open a new vein of research based on glassy disordered dipolar composites that act as macroscopic antenna with cooperative action; furthermore, these results have important implications for new design rules of tailored photonics.

Self-assembled monolayer field-effect transistors (SAMFETs) are not only a promising type of organic electronic device but also allow detailed analyses of structure-property correlations. The influence of the morphology on the charge transport is particularly pronounced, due to the confined monolayer of 2D-π-stacked organic semiconductor molecules. The morphology, in turn, is governed by relatively weak van-der-Waals interactions and is thus prone to dynamic structural fluctuations. Accordingly, combining electronic and physical characterization and time-averaged X-ray analyses with the dynamic information available at atomic resolution from simulations allows us to characterize self-assembled monolayer (SAM) based devices in great detail. For this purpose, we have constructed transistors based on SAMs of two molecules that consist of the organic p-type semiconductor benzothieno[3,2-b][1]benzothiophene (BTBT), linked to a C or C alkylphosphonic acid. Both molecules form ordered SAMs; however, our experiments show that the size of the crystalline domains and the charge-transport properties vary considerably in the two systems. These findings were confirmed by molecular dynamics (MD) simulations and semiempirical molecular-orbital electronic-structure calculations, performed on snapshots from the MD simulations at different times, revealing, in atomistic detail, how the charge transport in organic semiconductors is influenced and limited by dynamic disorder.

The use of functional oligomers of π-conjugated oligofluorenes led to a region-selective assembly of amorphous monolayers which exhibit robust lateral charge transport pathways in self-assembled monolayer field-effect transistors over long distances and even in mixed monolayers of semiconducting and insulating molecules. This oligomer concept might stimulate a new molecular design of self-assembling semiconducting materials.

Self‐assembled monolayers (SAMs) of π‐conjugated molecules can achieve robust charge transport by the formation of ordered 2D layers at the desired regions, which enable their application for organic integrated circuits. Here, the self‐assembled monolayer field‐effect transistor concept is applied as a scalable method to realize fully integrated complementary inverters by stepwise semiconductor deposition. Two‐component stacked bilayer ambipolar transistors are fabricated by semiconducting self‐assembled monolayers (n‐SAM or p‐SAM) as the bottom layer and a complementary thin‐film semiconductor layer on top. The integrated complementary metal‐oxide‐semiconductor like (CMOS‐like) inverter achieves proper logic performances. The nanometer‐thin monolayers exhibit effective charge transport and their flat, homogeneous surfaces benefit the interconnected growth of the top layer. Furthermore, by controlling the solution‐based and region‐selective deposition of p‐ and n‐type SAMs, fully integrated CMOS inverters are realized on wafer scale by photolithography for the first time. The CMOS inverters show a nearly 100% yield with a gain up to 48, and noise margin 3.68 V (73.6% of VDD/2). The strategy of semiconducting SAMs for digital logic gates demonstrates a reliable approach for sophisticated large‐area circuits.

Semiconducting self-assembled monolayers (SAMs) represent highly relevant components for the fabrication of organic thin-film electronics because they enable the precise formation of active π-conjugates in terms of orientation and layer thickness. In this work, we demonstrate self-assembled monolayer field-effect transistors (SAMFETs) composed of phosphonic acid oligomers of 3-hexylthiophene (oligothiophenesOT) with systematic variations of thiophene repeating units (5, 10, and 20). The devices exhibit stable lateral charge transport with increased mobility as a function of thiophene unit counts. Importantly, our work reveals the packing and intermolecular order of varied-chain-length SAMs at the molecular scale via X-ray reflectivity (XRR) and quantitative X-ray photoelectron spectroscopy (XPS). Short oligomers (OT5-PA and OT10-PA) arrange almost perpendicular to the substrate, forming highly ordered SAMs, whereas the long-chain OT20-PA exhibits a folded structure. By tuning the molecular order in the monolayers via the SAM substitution reaction, the OT20-PA devices show a tripling in mobility.