Search

Electrostatic potentials strongly affect molecular energy levels and charge states, providing the fascinating opportunity of molecular gating. Their influence on molecular vibrations remains less explored. Here, we investigate Ethyl-Diaminodicyanoquinone molecules on a monolayer of MoS$_2$ on Au(111) using scanning tunneling and atomic force microscopy and spectroscopy. These molecules exhibit a large dipole moment in gas phase, which we find to (partially) persist on the MoS$_2$ monolayer. The self-assembled structures consist of chains, where the dipoles of neighboring molecules are aligned anti-parallel. Thanks to the decoupling efficiency of the molecular states from the metal by the MoS$_2$ interlayer, we resolve vibronic states of the molecules, which vary in intensity depending on the molecular surrounding. We suggest that the vibrations are strongly damped by electrostatic interactions with the environment.

Molecules consisting of a donor and an acceptor moiety can exhibit large intrinsic dipole moments. Upon deposition on a metal surface, the dipole may be effectively screened and the charge distribution altered due to hybridization with substrate electronic states. Here, we deposit Ethyl-Diaminodicyanoquinone molecules, which exhibit a large dipole moment in gas phase, on a Au(111) surface. Employing a combination of scanning tunneling microscopy and non-contact atomic force microscopy, we find that a significant dipole moment persists in the flat-lying molecules. Density-functional theory calculations reveal that the dipole moment is even increased on the metal substrate as compared to the gas phase. We also show that the local contact potential across the molecular islands is decreased by several tens of meV with respect to the bare metal. We explain this by the induced charge-density redistribution due to the adsorbed molecules, which confine the substrate's wavefunction at the interface. Our local measurements provide direct evidence of this so-called push-back or cushion effect at the scale of individual molecules., Comment: This document is the unedited Author's version of a Submitted Work that was subsequently accepted for publication in Journal of Physical Chemistry C

While the basal plane of graphene is inert, defects in it are centers of chemical activity. An attractive application of such defects is towards controlled functionalization of graphene with foreign molecules. However, the interaction of the defects with reactive environment, such as ambient, decreases the efficiency of functionalization and makes it poorly controlled. Here, we report a novel approach to generate, monitor with time resolution, and functionalize the defects $\textit{in situ}$ without ever exposing them to the ambient. The defects are generated by an energetic Argon plasma and their properties are monitored using $\textit{in situ}$ Raman spectroscopy. We find that these defects are functional, very reactive, and strongly change their density from $\approx 1\cdot10^{13} cm^{-2}$ to $\approx 5\cdot10^{11} cm^{-2}$ upon exposure to air. We perform the proof of principle $\textit{in situ}$ functionalization by generating defects using the Argon plasma and functionalizing them $\textit{in situ}$ using Ammonia functional. The functionalization induces the n-doping with a carrier density up to $5\cdot10^{12} cm^{-2}$ in graphene and remains stable in ambient conditions., Comment: 12 pages, 4 figures, including Supplementary Information with 6 pages, 6 figures and 1 table

Graphene oxide can be used as a precursor to graphene but the quality of graphene flakes is highly heterogeneous. Scanning-Raman-Microscopy (SRM) is used to characterize films of graphene derived from flakes of graphene oxide with an almost intact carbon framework (ai-GO). The defect density of these flakes is visualized in detail by analyzing the intensity and full-width at half-maximum of the most pronounced Raman peaks. In addition, we superimpose the SRM results with AFM images and correlate the spectroscopic results with the morphology. Furthermore, we use SRM technique to display the amount of defects in a film of graphene. Thus, an area of 250 x 250 {\my}m2 of graphene is probed with a step-size increment of 1 {\mu}m. We are able to visualize the position of graphene flakes, edges and the substrate. Finally, we alter parameters of measurement to analyze the quality of graphene fast and reliable. The described method can be used to probe and visualize the quality of graphene films.

The chemical production of graphene as well as its controlled wet- chemical modification is a challenge for synthetic chemists and the characterization of reaction products requires sophisticated analytic methods. In this review we first describe the structure of graphene and graphene oxide. We then outline the most important synthetic methods which are used for the production of these carbon based nanomaterials. We summarize the state-of-the-art for their chemical functionalization by non-covalent and covalent approaches. We put special emphasis on the differentiation of the terms graphite, graphene, graphite oxide and graphene oxide. An improved fundamental knowledge about the structure and the chemical properties of graphene and graphene oxide is an important prerequisite for the development of practical applications.

In this study, we use our recently prepared graphene oxide (GO) with an almost intact {\sigma}-framework of C-atoms (ai-GO) to probe the thermal stability of the carbon framework for the first time. Ai-GO exhibits few defects only by preventing CO2 formation during synthesis. Ai-GO was thermally treated before chemical reduction and subsequently the resulting defect density in graphene was determined by statistical Raman microscopy. Surprisingly, the carbon framework of ai-GO is stable in thin films up to 100 {\deg}C. Furthermore, we find evidence for an increasing quality of ai-GO upon annealing at 50 {\deg}C before reduction. The carbon framework of GO prepared according to the popular Hummers method (GO-c)appears to be less stable and decomposition starts at 50 {\deg}C what is qualitatively indicated by CO2-trapping experiments in {\mu}m-thin films. Information about the stability of GO is important for storing, processing and applying GO in applications.

Monolayer transition metal dichalcogenides (TMDs) show an optimal surface-to-volume ratio and are thus promising candidates for novel molecule sensor devices. It was recently predicted that a certain class of molecules exhibiting a large dipole moment can be detected through the activation of optically inaccessible (dark) excitonic states in absorption spectra of tungsten-based TMDs. In this work, we investigate the molecule signatures in photoluminescence spectra in dependence of a number of different experimentally accessible quantities, such as excitation density, temperature as well as molecular characteristics including the dipole moment and its orientation, molecule-TMD distance, molecular coverage and distribution. We show that under certain optimal conditions, even room temperature detection of molecules can be achieved.