Estimation of π-π Electronic Couplings from Current Measurements

The - interactions between organic molecules are among the most important parameters for optimizing the transport and optical properties of organic transistors, light-emitting diodes, and (bio-)molecular devices. Despite substantial theoretical progress, direct experimental measurement of the - electronic coupling energy parameter t has remained an old challenge due to molecular structural variability and the large number of parameters that affect charge transport. Here, we propose a study of - interactions from electrochemical and current measurements on a large array of ferrocene-thiolated gold nanocrystals. We confirm the theoretical prediction that t can be assessed from a statistical analysis of current histograms. The extracted value of t ≈ 35 meV is in the expected range based on our density functional theory analysis. Furthermore, the t distribution is not necessarily Gaussian and could be used as an ultrasensitive technique to assess intermolecular distance fluctuation at the sub-angstrom level. The present work establishes a direct bridge between quantum chemistry, electrochemistry, organic electronics, and mesoscopic physics, all of which were used to discuss results and perspectives in a quantitative manner

F Center Mediated Growth of Patterned Organic Semiconductor Films on Alkali Halides

Organic semiconductors combine flexible tailoring of their optoelectronic properties by synthetic means with strong light matter coupling, which is advantageous for organic electronic device applications. Although spatially selective deposition has been demonstrated, lateral patterning of organic films with simultaneous control of molecular and crystalline orientation is lacking as traditional lithography is not applicable. Here, a new patterning approach based on surface localized F centers halide vacancies generated by electron irradiation of alkali halides is presented, which allows structural control of molecular adlayers. Combining optical and atomic force microscopy, X ray diffraction, and density functional theory DFT calculations, it is shown that dinaphthothienothiophene DNTT molecules adopt an upright orientation on pristine KCl surfaces, while the F centers stabilize a recumbent orientation, and that these orientations are maintained in thicker films. This specific nucleation results also in different crystallographic morphologies, namely, densely packed islands and jagged fibers, each epitaxially aligned on the KCl surface. Spatially selective surface irradiation can also be used to create patterns of F centers and thus laterally patterned DNTT films, which can be further transferred to any including elastomer substrate due to the water solubility of the alkali halide growth template

Dynamically Switching the Electronic and Electrostatic Properties of Indium Tin Oxide Electrodes with Photochromic Monolayers Toward Photoswitchable Optoelectronic Devices

The chemical modification of electrodes with organic materials is a common approach to tuning the electronic and electrostatic landscapes between interlayers in optoelectronic devices, thus facilitating charge injection at the electrode/semiconductor interfaces and improving their performance. The use of photochromic molecules for surface modification allows a dynamic control of the electronic and electrostatic properties of the electrode and thereby enables additional functionalities in such devices. Here, we show that the electronic properties of a transparent indium–tin oxide (ITO) electrode are reversibly and dynamically modified by depositing organic photochromic switches (diarylethenes) in the form of self-assembled monolayers (SAMs). By combining a range of surface characterization and density functional theory calculations, we present a detailed picture of the SAM binding to ITO, the packing density of molecules, their orientation, and work function modification of the ITO surface due to SAM deposition. Upon illumination with UV and green light, we observe a reversible shift of the frontier occupied levels by 0.7 eV and concomitantly a reversible work function change of ca. 60 meV. Our results prove the viability of dynamic switching of the electronic properties of the electrode with external light stimuli upon modification with a monolayer of photochromic molecules, which could be used to fabricate ITO-based photoswitchable optoelectronic devices