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.
The World Health Organization reported that 4.2 million deaths every year were a direct result of exposure to ambient air pollution (NO 2 , SO 2 , NH 3 , CO 2 , CO, CH 4 ). There is a well-demonstrated global need for high sensitivity, low cost and low energy consumption miniaturised gas sensors to be deployed in a dense network and to be used in an attempt to pinpoint and avoid high pollution hot spots. The high sensitivity of graphene to the local environment has shown to be highly advantageous in sensing applications, where ultralow concentrations of adsorbed molecules induce a significant response on the electronic properties of graphene. This is commonly attributed to the π electrons of graphene, being directly exposed to the surrounding environment. The unique electronic structure makes graphene the 'ultimate' sensing material for applications in environmental monitoring and air quality. In this review, we present the frontiers of graphene-based sensors considering both electrical and optical methods of detection and discuss the topical progress in an attempt to establish whether graphene can be considered as the ideal sensing material. We pay special attention to the optimization of the sensor performance, using various graphene hybrids and doping mechanisms. Furthermore, we present the recent developments in other 2D material-based sensors that have followed in the wake of graphene. We discuss the benchmarked parameters of graphene sensors, such as sensitivity, selectivity, response/recovery time and detection limit, and compare them with other 2D materials as well as existing state-of-the-art sensors currently being used in the field. We also perform a brief market analyses for the environmental sensing industry as well as provide a Strengths-Weaknesses-Opportunities-Threats analysis of graphene technology for environmental sensing.
We investigate the local surface potential and Raman characteristics of as-grown and ex-situ hydrogen intercalated quasi-free standing graphene on 4H-SiC(0001) grown by chemical vapor deposition. Upon intercalation, transport measurements reveal a change in the carrier type from n- to p-type, accompanied by a more than three-fold increase in carrier mobility, up to μh ≈ 4540 cm2 V−1 s−1. On a local scale, Kelvin probe force microscopy provides a complete and detailed map of the surface potential distribution of graphene domains of different thicknesses. Rearrangement of graphene layers upon intercalation to (n + 1)LG, where n is the number of graphene layers (LG) before intercalation, is demonstrated. This is accompanied by a significant increase in the work function of the graphene after the H2-intercalation, which confirms the change of majority carriers from electrons to holes. Raman spectroscopy and mapping corroborate surface potential studies.
Light emission in atomically thin heterostructures is known to depend on the type of materials and the number and stacking sequence of the constituent layers. Here we show that the thickness of a two-dimensional substrate can be crucial in modulating the light emission. We study the layer-dependent charge transfer in vertical heterostructures built from monolayer tungsten disulfide (WS2) on one- and two-layer epitaxial graphene, unravelling the effect that the interlayer electronic coupling has on the excitonic properties of such heterostructures. We bring evidence that the excitonic properties of WS2 can be effectively tuned by the number of supporting graphene layers. Integrating WS2 monolayers with two-layer graphene leads to a significant enhancement of the photoluminescence response, up to 1 order of magnitude higher compared to WS2 supported on one-layer graphene. Our findings highlight the importance of substrate engineering when constructing atomically thin-layered heterostructures.
We demonstrate proof-of-concept graphene sensors for environmental monitoring of ultralow concentration NO in complex environments. Robust detection in a wide range of NO concentrations, 10-154 ppb, was achieved, highlighting the great potential for graphene-based NO sensors, with applications in environmental pollution monitoring, portable monitors, automotive and mobile sensors for a global real-time monitoring network. The measurements were performed in a complex environment, combining NO/synthetic air/water vapor, traces of other contaminants, and variable temperature in an attempt to fully replicate the environmental conditions of a working sensor. It is shown that the performance of the graphene-based sensor can be affected by coadsorption of NO and water on the surface at low temperatures (≤70 °C). However, the sensitivity to NO increases significantly when the sensor operates at 150 °C and the cross-selectivity to water, sulfur dioxide, and carbon monoxide is minimized. Additionally, it is demonstrated that single-layer graphene exhibits two times higher carrier concentration response upon exposure to NO than bilayer graphene.
Confocal laser scanning microscopy (CLSM) is a non-destructive, highly-efficient optical characterization method for large-area analysis of graphene on different substrates, which can be applied in ambient air, does not require additional sample preparation, and is insusceptible to surface charging and surface contamination. CLSM leverages optical properties of graphene and provides greatly enhanced optical contrast and mapping of thickness down to a single layer.We demonstrate the effectiveness of CLSM by measuring mechanically exfoliated and chemical vapor deposition graphene on Si/SiO2, and epitaxial graphene on SiC. In the case of graphene on Si/SiO2, both CLSM intensity and height mapping is powerful for analysis of 1-5 layers of graphene. For epitaxial graphene on SiC substrates, the CLSM intensity allows us to distinguish features such as dense, parallel 150 nm wide ribbons of graphene (associated with the early stages of the growth process) and large regions covered by the interfacial layer and 1-3 layers of graphene.In both cases, CLSM data shows excellent correlation with conventional optical microscopy, atomic force microscopy, Kelvin probe force microscopy, conductive atomic force microscopy, influence on the layer growth and uniformity 5,32 . Recently, KPFM was shown to be a more reliable method for distinguishing the number of EG layers 33 . Nonetheless, Raman and SPM methods are time consuming and typically limit the scan size to a few tens of micrometers. Scaling up the production process requires fast and accurate characterization of the material quality at the wafer scale, while at the same time retaining sub-micrometer spatial resolution.In this report, we demonstrate that reflection mode CLSM is a superior tool for rapid characterization of large-area graphene and graphene nanostructures on Si/SiO2 and SiC, compared to conventional optical microscopy (OM), Raman spectroscopy, AFM, conductive atomic force microscopy (C-AFM), KPFM, and scanning electron microscope (SEM) methods.CLSM can simultaneously produce intensity and topography images as well as has a lateral resolution that can be pushed beyond the optical diffraction limit. The depth-of-field is enhanced by digitally selecting in-focus regions from multiple images at different focal planes, enabling high resolution over larger areas. First, we discuss CLSM results on various thicknesses of exfoliated graphene transferred to Si/SiO2 substrate. By comparing the results to AFM and Raman measurements, we present a method for assessing the CLSM intensity and height for graphene of different thicknesses. Next, we apply CLSM and Raman spectroscopy to CVD-grown graphene transferred to Si/SiO2 substrate to demonstrate fast and accurate, large-scale analysis. Finally, we apply CLSM to epitaxial graphene on SiC demonstrating the speed, accuracy, and versatility of CLSM compared to OM, SEM, AFM, KPFM, C-AFM and Raman microscopy. RESULTS Exfoliated graphene on Si/SiO2
The effects of humidity on the electronic properties of quasi-free standing one layer graphene (QFS 1LG) are investigated via simultaneous magneto-transport in the van der Pauw geometry and local work function measurements in a controlled environment. QFS 1LG on 4H-SiC(0001) is obtained by hydrogen intercalation of the interfacial layer. In this system, the carrier concentration experiences a two-fold increase in sensitivity to changes in relative humidity as compared to the as-grown epitaxial graphene. This enhanced sensitivity to water is attributed to the lowering of the hydrophobicity of QFS 1LG, which results from spontaneous polarization of 4H-SiC(0001) strongly influencing the graphene. Moreover, the superior carrier mobility of the QFS 1LG system is retained even at the highest humidity. The work function maps constructed from Kelvin probe force microscopy also revealed higher sensitivity to water for 1LG compared to 2LG in both QFS 1LG and as-grown systems. These results point to a new field of applications for QFS 1LG, i.e., as humidity sensors, and the corresponding need for metrology in calibration of graphene-based sensors and devices.
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