Modulating the Optoelectronic Properties of MoS2 by Highly Oriented Dipole-Generating Monolayers.

The noncovalent functionalization of two-dimensional materials (2DMs) with bespoke organic molecules is of central importance for future nanoscale electronic devices. Of particular interest is the incorporation of molecular functionalities that can modulate the physicochemical properties of the 2DMs via noninvasive external stimuli. In this study, we present the reversible modulation of the photoluminescence, spectroscopic properties (Raman), and charge transport characteristics of molybdenum disulfide (MoS2)-based devices via photoisomerization of a self-assembled monolayer of azobenzene-modified triazatriangulene molecules. The observed (opto)electronic modulations are explained by the n-type doping of the MoS2 lattice induced by the photoisomerization of the highly ordered azobenzene monolayer. This novel behavior could have profound effects on future composite 2DM-based (opto)electronics.

Dipole-Induced Raman Enhancement Using Noncovalent Azobenzene-Functionalized Self-Assembled Monolayers on Graphene Terraces.

Graphene is a promising material in the field of interface science, especially for noncovalent functionalization, sensing, and for applications in catalysis and nanoelectronics. The noncovalent self-assembly of aromatic molecules on graphene promotes electronic coupling through π-π interactions that allows for quenching of the fluorescence of adsorbent molecules and the enhancement of their Raman spectra via graphene-enhanced Raman spectroscopy (GERS). Although recent work has explored the Raman enhancement on mono- and bilayer graphene, the layer dependence of both electronic phenomena (i.e., fluorescence quenching and Raman enhancement) has largely remained underexplored. Similarly, the effect of near-surface molecular dipoles on GERS has sparsely been examined. In this work, we employ self-assembled monolayers of azobenzene-decorated triazatriangulene molecules (AzoTATA) on graphene terraces to examine the effect of switchable molecular dipoles on the GERS effect, which occurs as a function of azobenzene photoisomerization. Furthermore, using empirical and computational methods, we present a systematic study for deriving the mechanism of GERS enhancement and fluorescence quenching on graphene terraces.

Formation of Highly Ordered Self-Assembled Monolayers on Two-Dimensional Materials via Noncovalent Functionalization.

Functionalized two-dimensional materials (2DMs) are attracting much attention due to their promising applications in nanoscale devices. Producing continuous and homogeneous surface assemblies with a high degree of order has been challenging. In this work, we demonstrate that by noncovalently self-assembling molecular platforms on 2DMs, high-quality and highly ordered monolayers can be generated. The high degree of order and uniformity of the self-assembled monolayer layers were confirmed by a variety of analytic techniques including time-of-flight secondary ion mass spectrometry, scanning tunnelling microscopy, X-ray photoelectron spectroscopy, and atomic force microscopy. Furthermore, by selectively enhancing the molecular vibrations of the molecular platform, via a combination of graphene-enhanced Raman spectroscopy (GERS) and surface-enhanced Raman spectroscopy (SERS), we were able to determine the orientation of self-assembled molecular platforms with respect to the surface normal. The selective enhancement of the vibrational modes occurs by taking advantage of the distance dependence of the Raman enhancement either by the graphene surface (GERS) or the silver nanoparticules (SERS) that are located on top of the self-assembled monolayer.