Vibrational spectroscopies, such as Raman and Fouriertransform infrared spectroscopy (FT-IR), are powerful tools for the characterization of organic semiconductor thin films and crystals in addition to X-ray diffraction and scanning atomic force microscopy. They enable the investigation of molecular orientation, polymorphism, doping levels, and intra-as well as intermolecular vibrational modes albeit without much spatial resolution. Two fundamentally different scanning probe techniques offer two-dimensional mapping of infraredactive modes with a spatial resolution below 100 nm: scattering-type scanning near-field optical microscopy (IR s-SNOM) and atomic force microscopy-infrared spectroscopy (AFM-IR). Here, we compare these two techniques with each other and to conventional FT-IR spectroscopy measurements with regard to their applicability to highly ordered molecular semiconductors. For this purpose, we use organic single crystals of rubrene, perfluorobutyldicyanoperylene carboxydiimide (PDIF-CN 2 ), TIPS-pentacene, and TIPStetraazapentacene as model systems. We find significant spectral differences depending on the technique and polarization that are related to the anisotropy of the crystals and the fundamentally different working principles of the applied methods. The spatial and spectral resolution of IR s-SNOM and AFM-IR are further tested and compared for a polycrystalline thin film of PDIF-CN 2 .

Liquid phase exfoliation has evolved to an important and widely used production technique for 2D materials, giving access to large quantities of nanosheets in the liquid phase. Post-exfoliation size selection, for example by liquid cascade centrifugation, can be applied to tune nanosheet lateral sizes and thicknesses. Various starting materials from powders to high-quality crystals can be used for the process. However, the impact of the starting material on the dispersion quality and quantity is widely unexplored. Here, we performed liquid phase exfoliation combined with liquid cascade centrifugation on six different MoS2 starting materials and assessed nanosheet yield, lateral size, and layer number using established quantitative spectroscopic metrics. We show that both yield and nanosheet dimensions are widely unaffected by the choice of the starting material. In contrast, some impact is observed with respect to optical properties, such as photoluminescence of the monolayers. We find that the photoluminescence intensity is lower for small crystallite bulk materials.

In recent years, various functionalization strategies for transition-metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS 2 with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS 2 is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.

In recent years, various functionalization strategies for transition-metal dichalcogenides have been explored to tailor the properties of materials and to provide anchor points for the fabrication of hybrid structures. Herein, new insights into the role of the surfactant in functionalization reactions are described. Using the spontaneous reaction of WS 2 with chloroauric acid as a model reaction, the regioselective formation of gold nanoparticles on WS 2 is shown to be heavily dependent on the surfactant employed. A simple model is developed to explain the role of the chosen surfactant in this heterogeneous functionalization reaction. The surfactant coverage is identified as the crucial element that governs the dominant reaction pathway and therefore can severely alter the reaction outcome. This study shows the general importance of the surfactant choice and how detrimental or beneficial a certain surfactant can be to the desired functionalization.

Liquid phase exfoliation (LPE) is a popular method to create dispersions of two-dimensional nanosheets from layered inorganic van der Waals crystals. Here, it is applied to orthorhombic and triclinic single crystals of the organic semiconductor rubrene with only noncovalent interactions (mainly π–π) between the molecules. Distinct nanorods and nanobelts of rubrene are formed, stabilized against aggregation in aqueous sodium cholate solution, and isolated by liquid cascade centrifugation. Selected-area electron diffraction and Raman spectroscopy confirm the crystallinity of the rubrene nanorods and nanobelts while the optical properties (absorbance, photoluminescence) of the dispersions are similar to rubrene solutions due to their randomized orientations. The formation of these stable crystalline rubrene nanostructures with only a few molecular layers by LPE confirms that noncovalent interactions in molecular crystals can be strong enough to enable mechanical exfoliation similar to inorganic layered materials.