We compare the three most commonly used scanning probe techniques to obtain a reliable value of the work function in graphene domains of different thickness. The surface potential (SP) of graphene is directly measured in Hall bar geometry via a combination of electrical functional microscopy and spectroscopy techniques, which enables calibrated work function measurements of graphene domains in ambient conditions with values Φ1LG ~4.55 ± 0.02 eV and Φ2LG ~ 4.44 ± 0.02 eV for single- and bi-layer, respectively. We demonstrate that frequency-modulated Kelvin probe force microscopy (FM-KPFM) provides more accurate measurement of the SP than amplitude-modulated (AM)-KPFM. The discrepancy between experimental results obtained by different techniques is discussed. In addition, we use FM-KPFM for contactless measurements of the specific components of the device resistance. We show a strong non-Ohmic behavior of the electrode-graphene contact resistance and extract the graphene channel resistivity.

The sensitivity of graphene to the surrounding environment is given by its π electrons, which are directly exposed to molecules in the ambient. The high sensitivity of graphene to the local environment has shown to be both advantageous but also problematic for graphene-based devices, such as transistors and sensors, where the graphene carrier concentration and mobility change due to ambient humidity variations. In this review, recent progress in understanding the effects of water on different types of graphene, grown epitaxially and quasi-free standing on SiC, by chemical vapour deposition on SiO2, as well as exfoliated flakes, are presented. It is demonstrated that water withdraws electrons from graphene, but the graphene-water interaction highly depends on the thickness, layer stacking, underlying substrate and substrate-induced doping. Moreover, we highlight the importance of clear and unambiguous description of the environmental conditions (i.e. relative humidity) whenever a routine characterisation for carrier concentration and mobility is reported (often presented as a simple figure-of-merit), as these electrical characteristics are highly dependent on the adsorbed molecules and the surrounding environment.

Abstract:We present local electrical characterization of epitaxial graphene grown on both Si-and C-faces of 4H-SiC using Electrostatic Force Microscopy and Kelvin Probe Force Microscopy in ambient conditions and at elevated temperatures. These techniques provide a straightforward identification of graphene domains with various thicknesses on the substrate where topographical determination is hindered by adsorbates and SiC terraces. We also use Electrostatic Force Spectroscopy which allows quantitative surface potential measurements with high spatial resolution. Using these techniques, we study evolution of a layer of atmospheric water as a function of temperature, which is accompanied by a significant change of the absolute surface potential difference. We show that the nanoscale wettability of the material is strongly dependent on the number of graphene layers, where hydrophobicity increases with graphene thickness. We also use micron-sized graphene Hall bars with gold electrodes to calibrate work function of the electrically conductive probe and precisely and quantitatively define the work functions for single-and double-layer graphene.

We directly correlate the local (20-nm scale) and global electronic properties of a device containing mono-, bi-and tri-layer epitaxial graphene (EG) domains on 6H-SiC(0001) by simultaneously performing local surface potential measurements using Kelvin probe force microscopy and global transport measurements. Using well-controlled environmental conditions, where the starting state of the surface can be reproducibly defined, we investigate the doping effects of N2, O2, water vapour and NO2 at concentrations representative of the ambient air. We show that presence of O2, water vapour and NO2 leads to p-doping of all EG domains. However, the thicker layers of EG are significantly less affected by the atmospheric dopants. Furthermore, we demonstrate that the general consensus of O2 and water vapour present in ambient air providing majority of the p-doping to graphene is a common misconception. We experimentally show that even the combined effect of O2, water vapour, and NO2 at concentrations higher than typically present in the atmosphere does not fully replicate the state of the EG surface in ambient air. All doping effects can be reproducibly reversed by vacuum annealing. Thus, for EG gas sensors it is essential to consider naturally occurring environmental effects and properly separate them from those coming from targeted species.

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The presence of grain boundaries in two-dimensional (2D) materials is known to greatly affect their physical, electrical, and chemical properties. Given the difficulty in growing perfect large single-crystals of 2D materials, revealing the presence and characteristics of grain boundaries becomes an important issue for practical applications. Here, we present a method to visualize the grain structure and boundaries of 2D materials by epitaxially growing transition metal dichalcogenides (TMDCs) over them. Triangular single-crystals of molybdenum disulfide (MoS2) epitaxially grown on the surface of graphene allowed us to determine the orientation and size of the graphene grains. Grain boundaries in the polycrystalline graphene were also visualized reflecting their higher chemical reactivity than the basal plane. The method was successfully applied to graphene field-effect transistors, revealing the actual grain structures of the graphene channels. Moreover, we demonstrate that this method can be extended to determine the grain structure of other 2D materials, such as tungsten disulfide (WS2). Our visualization method based on van der Waals epitaxy can offer a facile and large-scale labeling technique to investigate the grain structures of various 2D materials, and it will also contribute to understand the relationship between their grain structure and physical properties.

Aligned growth of transition metal dichalcogenides and related two-dimensional (2D) materials is essential for the synthesis of high-quality 2D films due to effective stitching of merging grains. Here, we demonstrate the controlled growth of highly aligned molybdenum disulfide (MoS) on c-plane sapphire with two distinct orientations, which are highly controlled by tuning sulfur concentration. We found that the size of the aligned MoS grains is smaller and their photoluminescence is weaker as compared with those of the randomly oriented grains, signifying enhanced MoS-substrate interaction in the aligned grains. This interaction induces strain in the aligned MoS, which can be recognized from their high susceptibility to air oxidation. The surface-mediated MoS growth on sapphire was further developed to the rational synthesis of an in-plane MoS-graphene heterostructure connected with the predefined orientation. The in-plane epitaxy was observed by low-energy electron microscopy. Transmission electron microscopy and scanning transmission electron microscopy suggest the alignment of a zigzag edge of MoS parallel to a zigzag edge of the neighboring graphene. Moreover, better electrical contact to MoS was obtained by the monolayer graphene compared with a conventional metal electrode. Our findings deepen the understanding of the chemical vapor deposition growth of 2D materials and also contribute to the tailored synthesis as well as applications of advanced 2D heterostructures.

The sensitivity to water vapour of one-, two-, and three-layer epitaxial graphene (1, 2, and 3LG) is examined in this study. It is unambiguously shown that graphene's response to water, as measured by changes in work function and carrier density, is dependent on its thickness, with 1LG being the most sensitive to water adsorption and environmental concentration changes. This is furthermore substantiated by surface adhesion measurements, which bring evidence that 1LG is less hydrophobic than 2LG. Yet, surprisingly, it is found that other contaminants commonly present in ambient air have a greater impact on graphene response than water vapor alone. This study indicates that graphene sensor design and calibration to minimize or discriminate the effect of the ambient, in which it is intended to operate, are necessary to insure the desired sensitivity and reliability of sensors. The present work will aid in developing models for realistic graphene sensors and establishing protocols for molecular sensor design and development.