Nitrogen dioxide (NO₂) is a potential hazard to human health at low concentrations, below one part per million (ppm). NO₂ can be monitored using gas sensors based on multi-layered graphene operating at ambient temperature. However, reliable detection of concentrations on the order of parts per million and lower is hindered by partial recovery and lack of reproducibility of the sensors after exposure. We show how to overcome these longstanding problems using ultraviolet (UV) light. When exposed to NO₂, the sensor response is enhanced by 290 % − 550 % under a 275 nm wavelength light emitting diode irradiation. Furthermore, the sensor's initial state is completely restored after exposure to the target gas. UV irradiation at 68 W/m2 reduces the NO₂ detection limit to 30 parts per billion (ppb) at room temperature. We investigated sensor performance optimization for UV irradiation with different power densities and target gases, such as carbon oxide and ammonia. Improved sensitivity, recovery, and reproducibility of UV-assisted graphene-based gas sensors make them suitable for widespread environmental applications.

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In this study, we investigate a Schottky junction based on solution-processed multilayered graphene (MLG). We present a rectifying device obtained with a straightforward approach, that is drop-casting a few microliters of MLG solution simultaneously onto Si, Si-SiO2 and Si-SiO2-Cr/Au surface. Monitoring the modulation of Schottky barrier height while operating in reverse bias, we study the behavior of such prepared MLG-Si/junction (MLG-Si/J) when exposed to oxidizing atmosphere, especially to nitrogen oxide (NO2). We finally compare the sensing behavior of MLG-Si/J at 1 ppm of NO2 with that of a chemiresistor-based on similarly prepared solution-processed MLG. Our study thus opens the path towards low-cost highly sensitive graphene-based heterojunctions advantageously fabricated without any complexity in the technological process.

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Chemical vapor deposition (CVD) has been demonstrated as a highly promising technique for the production of graphene on large scale and enabling tunability of the intrinsic defects of the films during the synthesis.

In this work, we report on the correlation between the density of defects (DoD) and the kinetics of interaction of multi-layered graphene (MLG) with nitrogen dioxide (NO2) used as a target gas. We grow MLG on a pre-patterned molybdenum (Mo) catalyst layer, tailoring the DoD while growing MLG at temperatures from 850 °C to 980 °C. Analysing the Raman spectra, we show the lowering of the DoD as well as a quality dependence of MLG as a function of the growth temperature. The chemi-resistors based on MLG grown at different temperatures unambiguously highlight that, both during the exposure and the subsequent purge phase, the more defective the MLG, the more intense the NO2’s molecules interaction with MLG. Our results significantly mark a step forward in tuning the sensing properties of MLG without the need of any post-processing of the material after synthesis.@en

Chemical vapour deposition (CVD) has emerged as the dominant technique to combine high quality with large scale production of graphene. The key challenge for CVD graphene remains the transfer of the film from the growth substrate to the target substrate while preserving the quality of the material. Avoiding the transfer process of single or multi-layered graphene (SLG-MLG) has recently garnered much more interest. Here we report an original method to obtain a 4-inch wafer fully covered by MLG without any transfer step from the growth substrate. We prove that the MLG is completely released on the oxidized silicon wafer. A hydrogen peroxide solution is used to etch the molybdenum layer, used as a catalyst for the MLG growth via CVD. X-ray photoelectron spectroscopy proves that the layer of Mo is etched away and no residues of Mo are trapped beneath MLG. Terahertz transmission near-field imaging as well as Raman spectroscopy and atomic force microscopy show the homogeneity of the MLG film on the entire wafer after the Mo layer etch. These results mark a significant step forward for numerous applications of SLG-MLG on wafer scale, ranging from micro/nano-fabrication to solar cells technology.

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Humidity sensing is fundamental in some applications, as humidity can be a strong interferent in the detection of analytes under environmental conditions. Ideally, materials sensitive or insensitive towards humidity are strongly needed for the sensors used in the first or second case, respectively. We present here the sensing properties of multi-layered graphene (MLG) upon exposure to different levels of relative humidity. We synthesize MLG by chemical vapor deposition, as shown by Raman spectroscopy, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). Through an MLG-based resistor, we show that MLG is scarcely sensitive to humidity in the range 30%–70%, determining current variations in the range of 0.005%/%relative humidity (RH) well below the variation induced by other analytes. These findings, due to the morphological properties of MLG, suggest that defective MLG is the ideal sensing material to implement in gas sensors operating both at room temperature and humid conditions.

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A novel gas sensor based on multi-layered graphene (MLG) functionalised with gold nanoparticles (Au-NPs) is presented. We demonstrate for the first time that: (1) the signal saturates during the analyte exposure, something which does not occur in the pristine material and in graphene-based gas sensors in general; (2) the sign of the device current response is inverted. MLG is grown by chemical vapour deposition on pre-patterned CMOS-compatible Mo catalyst. The sensor is fabricated directly on the growth substrate, without any transfer of MLG. The Au-NPs are later deposited from an aerosol on the sensor at a specific controlled location, mitigating any additional patterning steps. The functionalised sensor is tested with 1 ppm (part-per-million) of NO2 at room temperature.@en

A method to grow multi layers graphene (MLG) just by thermal annealing in an inert atmosphere is reported. A molybdenum (Mo) catalyst layer is used in combination with a solid amorphous carbon (a-C) source on top or below the Mo layer. The formation of MLG directly on top of the catalyst substrate surface is confirmed by Raman spectroscopy, atomic force microscopy, cross-section transmission electron microscopy, electron energy loss spectroscopy and x-ray photoelectron spectroscopy. Growth of MLG on top of the Mo catalyst is demonstrated both with a-C below and above the Mo layer. The growth mechanism is attributed to the diffusion of a-C through the Mo layer and precipitation into the graphene at the surface, similar to the growth by chemical vapour deposition (CVD) on a Ni catalyst. The role of the inert Ar/H ₂ atmosphere, carbon thickness, catalyst thickness, anneal time and anneal temperature are reported. Fast growth of MLG (5 min) at 915 °C is demonstrated. The quality of MLG prepared by thermal annealing is at least as good as that of MLG synthesized by CVD. The relevant achievements presented in this study make the proposed technique a promising alternative to CVD based MLG.

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Limitations such as lack of detected stationary signal and slow signal recovery after detection currently affect graphene-based chemi-sensors operating at room temperature. In this work, we model the behavior of a sensor in a test chamber having limited volume and simulating the environmental conditions. From this model, we mathematically derive the calibration method for the sensor. The approach, focused on the time differential of the signal output, is tested on multi-layered graphene (MLG)-based sensors towards the chosen target gas (nitrogen dioxide) in the range from 0.12 to 1.32 ppm. MLG acting as sensing layer is synthesized by chemical vapor deposition. Our study paves the route for a wider applicability of the analysis to calibrate the class of devices affected by non-stationary and recovery issues.@en

In this paper we report on gas sensors based on graphene grown by Chemical Vapor Deposition at 850 °C. Mo was used as catalyst for graphene nucleation. Resistors were directly designed on pre-patterned Mo using the transfer-free process we recently developed, thus avoiding films damage during the transfer to the target substrate. Devices operating at room temperature and relative humidity set at 50% were tested towards NO2. The sensors resulted to be highly specific towards NO2 and showed current variation up to 6%. The performances were compared with those of gas sensors based on graphene grown at 980 °C, which represents the usual growth temperature for such material. The findings show that by lowering the graphene growth temperature and consequently the energy consumptions the sensing benefits of these devices are still preserved.@en

In this work, we present an innovative method which enables to solve fundamental limitations affecting graphene-based chemi-sensors operating under environmental conditions, namely the lack of signal saturation and the scarce recovery after the detection step. The method, which exploits the differential current instead of the current itself, is validated by applying it on different devices having an exposed area equal to 512 pm2. The analysis is performed by adopting nitrogen dioxide (NO2) as target gas in the range from 0.12 ppm to 1.5 ppm. The approach reliability is further confirmed by performing sensing tests towards NO2 with the relative humidity set at two different levels, 30% and 50%.@en

The crystal structure of graphene flakes is expected to significantly affect their sensing properties. Here we report an experimental investigation on the crystalline structure of graphene aimed at exploring the effects on the gas sensing properties. The morphology of graphene, prepared via Chemical Vapor Deposition (CVD), Liquid Phase Exfoliation (LPE) and Mechanical Exfoliation (ME), is inspected through Raman spectroscopy, Atomic Force Microscopy (AFM) and Scanning Electron Microscopy (SEM). CVD and LPE-graphene structures are found to be more defective with respect to ME-graphene. The defects are due to the jagged morphology of the films rather than originating from intrinsic disorder. The flatness of ME-graphene flakes, instead, explains the absence of defects. Chemiresistors based on the three different graphene preparation methods are subsequently exposed to NO2 in the concentration range 0.1–1.5 ppm (parts per million). The device performance is demonstrated to be strongly and unambiguously affected by the material structure: the less defective the material is, the higher the response rate is. In terms of signal variation, at 1.5 ppm, for instance, ME-graphene shows the highest value (5%) among the three materials. This study, comparing simultaneously graphene and sensors prepared via different routes, provides the first experimental evidence of the role played by the graphene level of defectiveness in the interaction with analytes. Moreover, these findings can pave the path for tailoring the sensor behavior as a function of graphene morphology.@en

The work herein presented investigates the behavior of graphene-based gas sensors realized by using an innovative way to prepare graphene. The sensing layer was directly grown by chemical vapor deposition on pre-patterned CMOS compatible Mo catalyst and then it was eased on the underlying SiO2 through a completely transfer-free process. Devices with different geometries were designed and tested towards NO2 and NH3 in environmental conditions, i.e. room temperature and relative humidity set at 50%. Furthermore, these gas sensors were also calibrated, resulting in the ability to detect concentrations down to 240 ppb and 17 ppm of NO2 and NH3, respectively. These results are in agreement with the best performances reported in literature for graphene-based sensors. They not only confirm the successful devices fabrication through the transfer-free approach, but also pave the route for large-scale production of MEMS/NEMS sensors.@en