We present a method to monitor methane at atmospheric concentrations with errors inthe order of tens of parts per billion. We use machine learning techniques and periodic calibrationswith reference equipment to quantify methane from the readings of an electronic nose. The resultsobtained demonstrate versatile and robust solution that outputs adequate concentrations in a varietyof different cases studied, including indoor and outdoor environments with emissions arising fromnatural or anthropogenic sources. Our strategy opens the path to a wide-spread use of low-costsensor system networks for greenhouse gas monitoring.

We present an electronic nose that detects ovarian cancer based on gas emissions from blood plasma. There is currently no test available for screening or diagnostic testing of this disease, whichis therefore often detected at aa late stage, resulting in a poor prognosis. Our approach correctly detected 85 out of 87 ovarian cancers, ranging from borderline to stage IV.

Reducing emissions of the key greenhouse gas methane (CH4) is increasingly highlighted as being important to mitigate climate change. Effective emission reductions require cost-effective ways to measure CH4 to detect sources and verify that mitigation efforts work. We present here a novel approach to measure methane at atmospheric concentrations by means of a low-cost electronic nose strategy where the readings of a few sensors are combined, leading to errors down to 33 ppb and coefficients of determination, R-2, up to 0.91 for in situ measurements. Data from methane, temperature, humidity, and atmospheric pressure sensors were used in customized machine learning models to account for environmental cross-effects and quantify methane in the ppm-ppb range both in indoor and outdoor conditions. The electronic nose strategy was confirmed to be versatile with improved accuracy when more reference data were supplied to the quantification model. Our results pave the way toward the use of networks of low-cost sensor systems for the monitoring of greenhouse gases.

We report on phase and strain changes in Ti_1-xAl_xN (0 ≤ x ≤ 0.61) coatings on cutting tools during turning recorded in operando by high-energy x-ray diffractometry. Orthogonal cutting of AISI 4140 steel was performed with cutting speeds of 360–370 m/min. Four positions along the tool rake face were investigated as a function of time in cut. Formation of γ-Fe in the chip reveals that the temperature exceeds 727 °C between the tool edge and the middle of the contact area when the feed rate is 0.06 mm/rev. Spinodal decomposition and formation of wurtzite AlN occurs at the positions of the tool with the highest temperature for the x ≥ 0.48 coatings. The strain evolution in the chip reveals that the mechanical stress is largest closest to the tool edge and that it decreases with time in cut for all analyzed positions on the rake face. The strain evolution in the coating varies between coatings and position on the rake face of the tool and is affected by thermal stress as well as the applied mechanical stress. Amongst others, the strain evolution is influenced by defect annihilation and, for the coatings with highest Al-content (x ≥ 0.48), phase changes.

Food allergies are hypersensitivity immune responses triggered by (traces of) allergenic compounds in foods and drinks. The recent trend towards plant-based and lactose-free diets has driven an increased consumption of plant -based milks (PBMs) with the risk of cross-contamination of various allergenic plant-based proteins during the food manufacturing process. Conventional allergen screening is usually performed in the laboratory, but portable biosensors for on-site screening of food allergens at the production site could improve quality control and food safety. Here, we developed a portable smartphone imaging surface plasmon resonance (iSPR) biosensor composed of a 3D-printed microfluidic SPR chip for the detection of total hazelnut protein (THP) in commercial PBMs and compared its instrumentation and analytical performance with a conventional benchtop SPR. The smartphone iSPR shows similar characteristic sensorgrams compared with the benchtop SPR and enables the detection of trace levels of THP in spiked PBMs with the lowest tested concentration of 0.625 mu g/mL THP. The smartphone iSPR achieved LoDs of 0.53, 0.16, 0.14, 0.06, and 0.04 mu g/mL THP in 10x-diluted soy, oat, rice, coconut, and almond PBMs, respectively, with good correlation with the conventional benchtop SPR system (R2 0.950-0.991). The portability and miniaturized characteristics of the smartphone iSPR biosensor platform make it promising for the future on-site detection of food allergens by food producers.

High-throughput production methods such as screen printing can bring stretchable electronics out of the lab into the market. Most stretchable conductor inks for screen printing are based on silver nanoparticles or flakes due to their favorable performance-to-cost ratio, but silver is prone to tarnishing and corrosion, thereby limiting the stability of such conductors. Here, we report on a cost-efficient and scalable approach to resolve this issue by developing screen printable inks based on silver flakes chemically coated by a thin layer of gold. The printed stretchable AgAu conductors reach a conductivity of 8500 S cm-1, remain conductive up to 250% strain, show excellent corrosion and tarnishing stability, and are used to demonstrate wearable LED and NFC circuits. The reported approach is attractive for smart clothing, as the long-term functionality of such devices is expected in a variety of environments.

The design of a smartphone imaging surface plasmon resonance (Smart-iSPR) system integrated with an affordable 3D-printed microfluidic SPR chip fabricated via a facile manufacturing approach could pave the way towards the development of miniaturized and integrated smartphone iSPR biosensors for emerging point-of-use applications. Conventional smartphone-based SPR systems using soft photolithography for the fabrication of microfluidics SPR chips are costly, labour-intensive and required a specially-equipped light-controlled environment, that is inadequate and mismatched with the consumer-based smartphone detection platform. Herein, we report the design, fabrication and testing of an innovative print-and-stick unibody microfluidics coupled SPR chip for smartphone iSPR. The 3Dprinted microfluidics (~V0.006) is assembled via an aptly-sized adhesive tape with the gold SPR sensing surface. Such a simple integrated microfluidic SPR chip with the print-and-stick configuration has a high resistance to fluid leakages at the channel-to-sensor interface with pressure up to 66.9 Pa and the tubingto-inset interfaces with pressure up to 86.9 Pa. The smartphone iSPR platform weighs 138 g and with a dimension of around 70 x 60 x 40 mm3, and its performance was characterized using a standard Biacore (R) 02-microglobulin calibration kit. The sensorgrams obtained by the smartphone iSPR show all the typical characteristics for surface functionalization, association and dissociation events. The smartphone iSPR responds linearly to 02-microglobulin within the range of 10-200 nM (R2 = 0.986) with a limit-ofdetection (LOD) of 1.5 nM. Given the miniaturized feature and simple camera-based imaging smartphone iSPR, the analytical performance is satisfactory when compared with the analytical dynamic range of 2 -32 nM described in the Biacore (R) protocol.(c) 2022 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

In this work, we demonstrate the application of terahertz-optical Hall effect (THz-OHE) to determine directionally dependent free charge carrier properties of ambient-doped monolayer and quasi-freestanding-bilayer epitaxial graphene on 4H-SiC(0001). Directionally independent free hole mobility parameters are found for the monolayer graphene. In contrast, anisotropic hole mobility parameters with a lower mobility in direction perpendicular to the SiC surface steps and higher along the steps in quasifree-standing-bilayer graphene are determined for the first time. A combination of THz-OHE, nanoscale microscopy and optical spectroscopy techniques are used to investigate the origin of the anisotropy. Different defect densities and different number of graphene layers on the step edges and terraces are ruled out as possible causes. Scattering mechanisms related to doping variations at the step edges and terraces as a result of different interaction with the substrate and environment are discussed and also excluded. It is suggested that the step edges introduce intrinsic scattering in quasi-free-standing-bilayer graphene, that is manifested as a result of the higher ratio between mean free path and average terrace width parameters. The suggested scenario allows to reconcile existing differences in the literature regarding the anisotropic electrical transport in epitaxial graphene. (C) 2020 The Authors. Published by Elsevier Ltd. This is an open access article under the CC BY license.

In this study, epitaxial graphene (EG) was grown on a 6H-SiC (0001) substrate via the thermal decomposition of SiC. Undoped and Cl- or N-doped molybdenum disulfide (MoS2) and tungsten disulfide (WS2) ultrathin films were spin-coated on the graphene surface. The scanning electron microscopy (SEM) images and topological atomic force microscopy (AFM) analysis showed good distribution of thin MoS2 and WS2 flakes on the EG surface. The X-ray photoelectron spectroscopy (XPS) confirmed the presence of Mo-related peaks of 3d(5/2) and 3d(3/2) at similar to 232.2 eV and 235.1 eV, respectively. It also represented peaks of W 4f(7/2) and 5p(5/2) at around 36.1 eV and 37.9 eV, respectively. Moreover, XPS results showed peaks at around 167.4 eV and 168.4 eV corresponding to S 2p for MoS2 and WS2, respectively. The XPS results also confirmed the presence of dopant elements in MoS2 and WS2 flakes. We fabricated sensors using undoped and chlorine- or nitrogen-doped MoS2 and WS2 ultrathin films for gas-sensing applications. These sensors were surveyed for ammonia (NH3) and nitrogen dioxide (NO2) gas sensing. As in NO2, both undoped sensors react with a decrease in relative sensor responses to NH3, hence showing n-type behavior. Doping MoS2 and WS2 with chlorine led to a higher response vis-a-vis the nitrogendoped sensors. The absolute relative response of Cl-doped WS2 and MoS2 was about 3.5 and 1.8 times more than that of their undoped counterparts toward NH3. A change of direction with a slightly smaller response (approximately x 0.8), however, could also be observed in the doping of MoS2 and WS2 with nitrogen. When exposed to NO2, the Cl-doped WS2 sensor response was 1.2 more than the N-doped one, while for MoS2 these values changed in the range of 1.2 - 1.6 for different flows of gas.

Boosting the sensitivity of solid-state gas sensors by incorporating nanostructured materials as the active sensing element can be complicated by interfacial effects. Interfaces at nanoparticles, grains, or contacts may result in nonlinear current-voltage response, high electrical resistance, and ultimately, electric noise that limits the sensor read-out. This work reports the possibility to prepare nominally one atom thin, electrically continuous platinum layers by physical vapor deposition on the carbon zero layer (also known as the buffer layer) grown epitaxially on silicon carbide. With a 3-4 angstrom thin Pt layer, the electrical conductivity of the metal is strongly modulated when interacting with chemical analytes, due to charges being transferred to/from Pt. The strong interaction with chemical species, together with the scalability of the material, enables the fabrication of chemiresistor devices for electrical read-out of chemical species with sub part-per-billion (ppb) detection limits. The 2D system formed by atomically thin Pt on the carbon zero layer on SiC opens up a route for resilient and high sensitivity chemical detection, and can be the path for designing new heterogenous catalysts with superior activity and selectivity.

For many applications, gas sensors need to be very sensitive, selective and exhibit a good stability. Moreover, they should also be cheap and small, and allow a fast response time. Usually, sensors are optimized for specific applications with a compromise between the mentioned criteria. Here, we show a method that allows very sensitive, but rather slow, graphene metal oxide hybrid sensors to be used in a much faster and more effective way with a focus on targeting trace level concentrations of some common toxic air pollutants. By exploiting the first-order time-derivative of the measured resistance signal after a concentration step, the response peak is achieved much faster, while also being more robust against sensor exposure and relaxation times, and concomitantly maintaining the very high sensitivities inherent to graphene. We propose to use this method to generate an additional signal to allow using sensors that are normally rather slow in applications where steep concentration changes need to be detected with much faster time constants.

In this manuscript, we explore the sensor properties of epitaxially grown graphene on silicon carbide decorated with nanolayers of CuO, Fe3O4, V2O5, or ZrO2. The sensor devices were investigated in regard to their response towards NH3 as a typical reducing gas and CO, C6H6, CH2O, and NO2 as gases of interest for air quality monitoring. Moreover, the impact of operating temperature, relative humidity, and additional UV irradiation as changes in the sensing environment have been explored towards their impact on sensing properties. Finally, a cross-laboratory study is presented, supporting stable sensor responses, and the final data is merged into a simplified sensor array. This study shows that sensors can be tailored not only by using different materials but also by applying different working conditions, according to the requirements of certain applications. Lastly, a combination of several different sensors into a sensor array leads to a well-performing sensor system that, with further development, could be suitable for several applications where there is no solution on the market today.

Surface functionalization has been shown to allow tailoring of graphene lattice thus making it suitable for different applications like sensing, supercapacitance devices, drug delivery system and memory devices. In this work, surface functionalization of epitaxial graphene on SiC (EG/SiC) was done by ion beam technology (30 keV Ag- ions at fluences ranging from 5 x 10(12) ions/cm(2) to 5 x 10(14) ions/cm(2)), which is one of the most precise techniques for introducing modifications in materials. Atomic force microscopy showed presence of nanostructures in ion implanted samples and Photoluminescence and X-ray photoelectron spectroscopy revealed that these are probably silicon oxy carbide. High-resolution transmission electron microscopy (HRTEM) showed decoupling of buffer layer from SiC substrate at many places in ion implanted samples. Further, HRTEM and Raman spectroscopy showed amorphization of both graphene and SiC at highest fluence. Fluence dependent increase in absorbance and resistance was observed. Gas sensors fabricated on pristine and ion implanted samples were able to respond to low concentration (50 ppb) of NO2 and NH3 gases. Detecting NH3 gas at low concentration further provides a simple platform for fabricating highly sensitive urea biosensor. We observed response inversion with increasing fluence along with presence of an optimal fluence, which maximized gas sensitivity of EG/SiC. (C) 2019 Elsevier Ltd. All rights reserved.

In this work, we investigated the sensing performance of epitaxial graphene on Si-face 4H-SiC (EG/SiC) for liquid-phase detection of heavy metals (e.g., Pb and Cd), showing fast and stable response and low detection limit. The sensing platform proposed includes 3D-printed microfluidic devices, which incorporate all features required to connect and execute lab-on-chip (LOC) functions. The obtained results indicate that EG exhibits excellent sensing activity towards Pb and Cd ions. Several concentrations of Pb2+ solutions, ranging from 125 nM to 500 mu M, were analyzed showing Langmuir correlation between signal and Pb2+ concentrations, good stability, and reproducibility over time. Upon the simultaneous presence of both metals, sensor response is dominated by Pb2+ rather than Cd2+ ions. To explain the sensing mechanisms and difference in adsorption behavior of Pb2+ and Cd2+ ions on EG in water-based solutions, we performed van-der-Waals (vdW)-corrected density functional theory (DFT) calculations and non-covalent interaction (NCI) analysis, extended charge decomposition analysis (ECDA), and topological analysis. We demonstrated that Pb2+ and Cd2+ ions act as electron-acceptors, enhancing hole conductivity of EG, due to charge transfer from graphene to metal ions, and Pb2+ ions have preferential ability to binding with graphene over cadmium. Electrochemical measurements confirmed the conductometric results, which additionally indicate that EG is more sensitive to lead than to cadmium.

Gases, such as nitrogen dioxide, formaldehyde and benzene, are toxic even at very low concentrations. However, so far there are no low-cost sensors available with sufficiently low detection limits and desired response times, which are able to detect them in the ranges relevant for air quality control. In this work, we address both, detection of small gas amounts and fast response times, using epitaxially grown graphene decorated with iron oxide nanoparticles. This hybrid surface is used as a sensing layer to detect formaldehyde and benzene at concentrations of relevance (low parts per billion). The performance enhancement was additionally validated using density functional theory calculations to see the effect of decoration on binding energies between the gas molecules and the sensor surface. Moreover, the time constants can be drastically reduced using a derivative sensor signal readout, allowing the sensor to work at detection limits and sampling rates desired for air quality monitoring applications.

Graphene in its pristine form has demonstrated a gas detection ability in an inert carrier gas. For practical use in ambient atmosphere, its sensor properties should be enhanced with functionalisation by defects and dopants, or by decoration with nanophases of metals or/and metal oxides. Excellent sensor behaviour was found for two types of single layer graphenes: grown by chemical vapour deposition (CVD) and transferred onto oxidized silicon (Si/SiO2/CVDG), and the epitaxial graphene grown on SiC (SiC/EG). Both graphene samples were functionalised using a pulsed laser deposited (PLD) thin V2O5 layer of average thickness approximate to 0.6 nm. According to the Raman spectra, the SiC/EG has a remarkable resistance against structural damage under the laser deposition conditions. By contrast, the PLD process readily induces defects in CVD graphene. Both sensors showed remarkable and selective sensing of NH3 gas in terms of response amplitude and speed, as well as recovery rate. SiC/EG showed a response that was an order of magnitude larger as compared to similarly functionalised CVDG sensor (295% vs. 31% for 100 ppm NH3). The adsorption site properties are assigned to deposited V2O5 nanophase, being similar for both sensors, rather than (defect) graphene itself. The substantially larger response of SiC/EG sensor is probably the result of the smaller initial free charge carrier doping in EG.

We report pulsed terahertz (THz) emission from solution-processed metal halide perovskite films with electric field 1 order of magnitude lower than p-InAs, an efficient THz emitter. Such emission is enabled by a unique combination of efficient charge separation, high carrier mobilities, and more importantly surface defects. The mechanism of generation was identified by investigating the dependence of the THz electric field amplitude on surface defect densities, excess charge carriers, excitation intensity and energy, temperature, and external electric field. We also show for the first time THz emission from a curved surface, which is not possible for any crystalline semiconductor and paves the way to focus high-intensity sources. These results represent a possible new direction for perovskite optoelectronics and for THz emission spectroscopy as a complementary tool in investigating surface defects on metal halide perovskites, of fundamental importance in the optimization of solar cells and light-emitting diodes.

Since even low concentrations of toxic heavy metals can seriously damage human health, it is important to develop simple, sensitive and accurate methods for their detection. Graphene, which is extremely sensitive to foreign species, is a key element in the development of a sensing platform where low concentrations of analyte have to be detected. This work discusses the proof of concept of a sensing platform for liquid-phase detection of heavy metals (e.g. Pb) based on epitaxial graphene sensors grown on Si-face 4H-SiC substrate (EG/SiC). The sensing platform developed includes a microfluidic chip incorporating all the features needed to connect and execute the Lab-on-chip (LOC) functions using 3D printing fast prototyping technology. Herein, we present the response of EG to concentrations of Pb2+ solutions ranging from 125 nM to 500 mu M, showing good stability and reproducibility over time and an enhancement of its conductivity with a Langmuir correlation between signal and Pb2+ concentration. Density functional theory (DFT) calculations are performed and clearly explain the conductivity changes and the sensing mechanism in agreement with the experimental results reported, confirming the strong sensitivity of the sensor to the lowest concentrations of the analyte. Furthermore, from the calibration curve of the system, a limit of detection (LoD) of 95 nM was extrapolated.

2D materials offer a unique platform for sensing with extreme sensitivity, since minimal chemical interactions cause noticeable changes in the electronic state. An area where this is particularly interesting is environmental monitoring of gases that are hazardous at trace levels. In this study, SiC is used as a base for epitaxial growth of high quality, uniform graphene, and for templated growth of atomically thin layers of platinum, with potential benefits in terms of the ability to operate at higher temperature and to serve as a more robust template for fiinctionalization compared to graphene. Fiinctionalization with nanoparticles allows tuning the sensitivity to specific molecules without damaging the 2D sensor transducer. With this platform we demonstrate detection of nitrogen dioxide, formaldehyde, and benzene at trace concentrations. This, combined with smart sensor signal evaluation allowing fast response times, could allow real-time monitoring of these toxic pollutants at concentrations of relevance to air quality monitoring.

ZnO films and nanostructures were deposited on Si substrates by MOCVD using single source solid state zinc acetylacetonate (Zn(AA)) precursor. Doping by silver was realized in-situ via adding 1 and 10 wt. % of Ag acetylacetonate (Ag(AA)) to zinc precursor. Influence of Ag on the microstructure, electrical and optical properties of ZnO at temperature range 220-550 degrees C was studied by scanning, transmission electron and Kelvin probe force microscopy, photoluminescence and four-point probe electrical measurements. Ag doping affects the ZnO microstructure via changing the nucleation mode into heterogeneous and thus transforming the polycrystalline films into a matrix of highly c-axis textured hexagonally faceted nanorods. Increase of the work function value from 4.45 to 4.75 eV was observed with Ag content increase, which is attributed to Ag behaviour as a donor impurity. It was observed, that near-band edge emission of ZnO NS was enhanced with Ag doping as a result of quenching deep-level emission. Upon high doping of ZnO by Ag it tends to promote the formation of basal plane stacking faults defect, as it was observed by HR TEM and PL study in the case of 10 wt.% of Ag. Based on the results obtained, it is suggested that NS deposition at lower temperatures (220-300 degrees C) is more favorable for p-type doping of ZnO. (C) 2018 Elsevier Ltd. All rights reserved.

Two-dimensional materials may constitute key elements in the development of a sensing platform where extremely high sensitivity is required, since even minimal chemical interaction can generate appreciable changes in the electronic state of the material. In this work, we investigate the sensing performance of epitaxial graphene on Si-face 4H-SiC (EG/SiC) for liquid-phase detection of heavy metals (e.g., Pb). The integration of preparatory steps needed for sample conditioning is included in the sensing platform, exploiting fast prototyping using a 3D printer, which allows direct fabrication of a microfluidic chip incorporating all the features required to connect and execute the Lab-on-chip (LOC) functions. It is demonstrated that interaction of Pb²⁺ ions in water-based solutions with the EG enhances its conductivity exhibiting a Langmuir correlation between signal and Pb²⁺ concentration. Several concentrations of Pb²⁺ solutions ranging from 125 nM to 500 µM were analyzed showing good stability and reproducibility over time.

Efficient ammonia gas sensor devices were fabricated based on nickel oxide (NiO) nanostructures films. Two chemical synthesis approaches were used: chemical spray pyrolysis (CSP) and chemical bath deposition (CBD), aiming at obtaining highly developed surface area and high chemical reactivity of NiO. Crystal structure, morphology, and composition of NiO films and nanostructures were investigated by scanning electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. CSP method results in the synthesis of NiO films with pure cubic crystalline structure of preferred orientation along (111) direction. The type of the precursors used (nickel acetate, nickel chloride and nickel nitrate) affects the morphology and crystallites average size of the deposited films. CBD method consisted of two stages: (i) deposition of nickel hydroxide phase and (ii) thermal annealing of nickel hydroxide at 450 A degrees C in air for 4 h. Resulted structures were nanoflakes, vertically arranged in a "wall-like" morphology. Fabricated structures were found to be sensitive to ammonia differently, depending on the synthesis approach and material morphology. NiO films deposited by CBD demonstrated a stable response to ammonia with maximum magnitude at the operating temperature of 300 A degrees C. The highest average response for the CBD-NiO sample was 114.3-141.3% for 25 and 150 ppm NH3, respectively, whereas the response range observed for the film processed by spray pyrolysis using nickel chloride was 31.7-142.5% for 25 and 150 ppm NH3, respectively.

It has been found that two-dimensional materials, such as graphene, can be used as remarkable gas detection platforms as even minimal chemical interactions can lead to distinct changes in electrical conductivity. In this work, epitaxially grown graphene was decorated with iron oxide nanoparticles for sensor performance tuning. This hybrid surface was used as a sensing layer to detect formaldehyde and benzene at concentrations of relevance in air quality monitoring (low parts per billion). Moreover, the time constants could be drastically reduced using a derivative sensor signal readout, allowing detection at the sampling rates desired for air quality monitoring applications.

In this study, we investigated means of performance enhancement in sensors based on epitaxial graphene on silicon carbide (SiC). Epitaxially grown graphene on SiC substrates were successfully decorated with metal oxide nanoparticles such as TiO2 and Fe3O4 using hollow cathode pulsed plasma sputtering. Atomic Force Microscopy and Raman data verified that no damage was added to the graphene surface. It could be shown that it was easily possible to detect benzene, which is one of the most dangerous volatile organic compounds, with the Fe3O4 decorated graphene sensor down to an ultra-low concentration of 5 ppb with a signal to noise ratio of 35 dB. Moreover, upon illumination with a UV light LED (265 nm) of the TiO2 decorated graphene sensor, the sensitivity towards a change of oxygen could be enhanced such that a clear sensor response could be seen which is a significant improvement over dark conditions, where almost no response occurred. As the last enhancement, the time derivative sensor signal was introduced for the sensor data evaluation, testing the response towards a change of oxygen. This sensor signal evaluation approach can be used to decrease the response time of the sensor by at least one order of magnitude. (C) 2018 Elsevier Ltd. All rights reserved.

Deep understanding of binding of toxic Lead (Pb) species on the surface of two-dimensional materials is a required prerequisite for the development of next-generation sensors that can provide fast and real-time detection of critically low concentrations. Here we report atomistic insights into the Lead behavior on epitaxial graphene (Gr) on silicon carbide substrates by thorough complementary study of voltammetry, electrical characterization, Raman spectroscopy, and Density Functional Theory (DFT). It is verified that the epitaxial graphene exhibits quasi-reversible anode reactions in aqueous solutions, providing a well-defined redox peak for Pb species and good linearity over a concentration range from 1 nM to 1 mu M. The conductometric approach offers another way to investigate Lead adsorption, which is based on the formations of stable charge-transfer complexes affecting the p-type conductivity of epitaxial graphene. Our results suggest the adsorption ability of the epitaxial graphene towards divalent Lead ions is concentration-dependent and tends to saturate at higher concentrations. To elucidate the mechanisms responsible for Pb adsorption, we performed DFT calculations and estimated the solvent-mediated interaction between Lead species in different oxidative forms and graphene. Our results provide central information regarding the energetics and structure of Pb-graphene interacting complexes that underlay the adsorption mechanisms of neutral and divalent Lead species. Such a holistic understanding favors design and synthesis of new sensitive materials for water quality monitoring.

Hydrophobic, self-doped conjugated polyelectrolytes (CPEs) are introduced as highly stable active materials for organic electrochemical transistors (OECTs). The hydrophobicity of CPEs renders films very stable in aqueous solutions. The devices operate at gate voltages around zero and show no signs of degradation when operated for 10(4) cycles under ambient conditions. These properties make the produced OECTs ideal devices for applications in bioelectronics.

In this work, we report a multi-scale investigation using several nano-, micro and macro-scale techniques of few layer graphene (FLG) sample consisting of large monolayer (ML) and bilayer (BL) areas grown on C-face 4H-SiC (000-1) by high-temperature sublimation. Single 1 x 1 diffraction patterns are observed by micro-low-energy electron diffraction for ML, BL and trilayer graphene with no indication of out-of-plane rotational disorder. A SiOx layer is identified between graphene and SiC by X-ray photoelectron emission spectroscopy and reflectance measurements. The chemical composition of the interface layer changes towards SiO2 and its thickness increases with aging in normal ambient conditions. The formation mechanism of the interface layer is discussed. It is shown by torsion resonance conductive atomic force microscopy that the interface layer causes the formation of non-ideal Schottky contact between ML graphene and SiC. This is attributed to the presence of a large density of interface states. Mid-infrared optical Hall effect measurements revealed Landau-level transitions in FLG that have a square-root dependence on magnetic field, which evidences a stack of decoupled graphene sheets. Contrary to previous works on decoupled C-face graphene, our BL and FLG are composed of ordered decoupled graphene layers without out-of-plane rotation. (C) 2017 Elsevier Ltd. All rights reserved.

In spite of the great expectations for epitaxial graphene (EG) on silicon carbide (SiC) to be used as a next-generation high-performance component in high-power nano- and micro-electronics, there are still many technological challenges and fundamental problems that hinder the full potential of EG/SiC structures and that must be overcome. Among the existing problems, the quality of the graphene/SiC interface is one of the most critical factors that determines the electroactive behavior of this heterostructure. This paper reviews the relevant studies on the carrier transport through the graphene/SiC, discusses qualitatively the possibility of controllable tuning the potential barrier height at the heterointerface and analyses how the buffer layer formation affects the electronic properties of the combined EG/SiC system. The correlation between the sp(2)/sp(3) hybridization ratio at the interface and the barrier height is discussed. We expect that the barrier height modulation will allow realizing a monolithic electronic platform comprising different graphene interfaces including ohmic contact, Schottky contact, gate dielectric, the electrically-active counterpart in p-n junctions and quantum wells.

In this work, surface functionalization of epitaxial graphene grown on silicon carbide was performed by ion irradiation to investigate their gas sensing capabilities. Swift heavy ion irradiation using 100 MeV silver ions at four varying fluences was implemented on epitaxial graphene to investigate morphological and structural changes and their effects on the gas sensing capabilities of graphene. Sensing devices are expected as one of the first electronic applications using graphene and most of them use functionalized surfaces to tailor a certain function. In our case, we have studied irradiation as a tool to achieve functionalization. Morphological and structural changes on epitaxial graphene layers were investigated by atomic force microscopy, Raman spectroscopy, Raman mapping and reflectance mapping. The surface morphology of irradiated graphene layers showed graphene folding, hillocks, and formation of wrinkles at highest fluence (2 x 10(13) ions/cm(2)). Raman spectra analysis shows that the graphene defect density is increased with increasing fluence, while Raman mapping and reflectance mapping show that there is also a reduction of monolayer graphene coverage. The samples were investigated for ammonia and nitrogen dioxide gas sensing applications. Sensors fabricated on pristine and irradiated samples showed highest gas sensing response at an optimal fluence. Our work provides new pathways for introducing defects in controlled manner in epitaxial graphene, which can be used not only for gas sensing application but also for other applications, such as electrochemical, biosensing, magnetosensing and spintronic applications. (C) 2017 Elsevier B.V. All rights reserved.

Metal Oxide Semiconductor (MOS) capacitor devices comprised of monolayer iron oxide-coated as well as non-coated polycrystalline Pt deposited on oxidized silicon carbide substrates have been fabricated and their usefulness as realistic model systems in catalyst studies development was evaluated. The CO oxidation characteristics of both iron oxide- and non-coated Pt catalysts were investigated using mass spectrometry, monitoring the carbon dioxide production rate for different combinations of carbon monoxide (CO) and oxygen concentrations at various temperatures. Additionally, the output capacitance of the MOS model catalysts was recorded for each individual CO oxidation activity. A low-temperature shift in CO oxidation characteristics for the monolayer-coated compared to the non-coated Pt catalysts was observed, similar to that previously reported for monolayer iron oxide grown on single-crystalline Pt substrates. A strong correlation between the output capacitance of the MOS structures and the CO oxidation characteristics was found for both monolayer- and non-coated model catalysts. Furthermore, the devices exhibit retained MOS electrical output and CO oxidation characteristics as well as an unaffected catalyst surface composition, as confirmed by photoelectron spectroscopy, even after 200 h of continuous model catalyst operation. In addition to the implications on practical applicability of monolayer iron oxide coating on widely used polycrystalline Pt films in real-world catalysts and sensors, the findings also point to new possibilities regarding the use of MOS model systems for in situ characterization, high throughput screening, and tailoring of e.g. catalyst- and fuel-cell-electrode materials for specific applications. (C) 2016 Elsevier Inc. All rights reserved.

Gas sensitive metal/metal-oxide field effect transistors based on silicon carbide were used to study the sensor response to benzene (C₆H₆) at the low parts per billion (ppb) concentration range. A combination of iridium and tungsten trioxide was used to develop the sensing layer. Highsensitivity to 10 ppb C₆H₆ was demonstrated during several repeated measurements at a constant temperature from 180 to 300 °C. The sensor performance was studied also as a function of the electrical operating point of the device, i.e., linear, onset of saturation, and saturation mode. Measurements performed in saturation mode gave a sensor response up to 52 % higher than those performed in linear mode.

This contribution treats the latest developments in the understanding of basic principles regarding device design, transduction mechanisms, gas-materials-interactions, and materials processing for the tailored design and fabrication of SiC FET gas sensor devices, mainly intended as products for the automotive sector.

Two-dimensional materials offer a unique platform for sensing where extremely high sensitivity is a priority, since even minimal chemical interaction causes noticeable changes inelectrical conductivity, which can be used for the sensor readout. However, the sensitivity has to becomplemented with selectivity, and, for many applications, improved response- and recovery times are needed. This has been addressed, for example, by combining graphene (for sensitivity) with metal/oxides (for selectivity) nanoparticles (NP). On the other hand, functionalization or modification of the graphene often results in poor reproducibility. In this study, we investigate thegas sensing performance of epitaxial graphene on SiC (EG/SiC) decorated with nanostructured metallic layers as well as metal-oxide nanoparticles deposited using scalable thin-film depositiontechniques, like hollow-cathode pulsed plasma sputtering. Under the right modification conditions the electronic properties of the surface remain those of graphene, while the surface chemistry can betuned to improve sensitivity, selectivity and speed of response to several gases relevant for airquality monitoring and control, such as nitrogen dioxide, benzene, and formaldehyde.

A vertical diode structure comprising homogeneous monolayer epitaxial graphene on silicon carbide is fabricated by thermal decomposition of a Si-face 4H-SiC wafer in argon atmosphere. Current-voltage characteristics of the graphene/SiC Schottky junction were analyzed by applying the thermionic-emission theory. Extracted values of the Schottky barrier height and the ideality factor are found to be 0.4879 +/- 0.013 eV and 1.01803 +/- 0.0049, respectively. Deviations of these parameters from average values are smaller than those of previously observed literature data, thereby implying uniformity of the Schottky barrier height over the whole diode area, a stable rectifying behaviour and a good quality of ohmic palladium-graphene contacts. Keeping in mind the strong sensitivity of graphene to analytes we propose the possibility to use the graphene/SiC Schottky diode as a sensing platform for the recognition of toxic heavy metals. Using density functional theory (DFT) calculations we gain insight into the nature of the interaction of cadmium, mercury and lead with graphene as well as estimate the work function and the Schottky barrier height of the graphene/SiC structure before and after applying heavy metals to the sensing material. A shift of the I-V characteristics of the graphene/SiC-based sensor has been proposed as an indicator of presence of the heavy metals. Since the calculations suggested the strongest charge transfer between Pb and graphene, the proposed sensing platform was characterized by good selectivity towards lead atoms and slight interferences from cadmium and mercury. The dependence of the sensitivity parameters on the concentration of Cd, Hg and Pb is studied and discussed.

Solid state phase of V7O16 with separate V2O5 phase were fabricated by pulsed laser deposition. The crystal structure and symmetry of the deposited films were studied with X-ray diffraction and Raman spectroscopy, respectively. Rietveld analysis was performed to the X-ray diffraction measurement results. The surface potentials and morphologies of the films were studied with atomic force microscopy, and microstructure of the thin films was analysed by transmission electron microscopy. Raman spectroscopy and Rietveld refinement results confirmed that the thin-film crystal structures varied between orthorombic V2O5 phase and another phase, triclinic V2016, previously found only in the walls of vanadium oxide nanotubes (VOx, -NT), bound together with organic amine. We have earlier presented the first results of stable and pure metal -oxide solid-state phase of V2016 manufactured from ceramic V205 target. Here we show more detailed study of these structures. The microstructure studies showed a variation on the porosity of the films according to crystal structures and also some fibre -like nanostructures were found in the films. The surface morphology depended strongly on the crystal structure and the surface potential studies showed 50 meV difference in the work function values between the phases. Compounds were found to be extremely sensitive towards ammonia, NH3, down to 40 ppb concentrations, and have shown to have the stability and selectivity to control the Selective Catalytic Reduction process, where nitrogen oxides are reduced by ammonia in, e.g. diesel exhausts.

High-temperature iridium-gated field effect transistors based on silicon carbide have been used for sensitive detection of specific volatile organic compounds (VOCs) in concentrations of health concern, for indoorair quality monitoring and control. Formaldehyde, naphthalene, and benzene were studied as hazardous VOCs at parts per billion (ppb) down to sub-ppb levels. The sensor performance and characteristics were investigated at a constant temperature of 330° C and at different levels of relative humidity up to 60 %, showing good stability and repeatability of the sensor response, and excellent detection limits in the sub-ppb range.

We report a single-step procedure for growth of ohmic Ti₃SiC₂ on 4H-SiC by sputter-deposition of Ti at 960 °C, based on the Ti–SiC solid-state reaction during deposition. X-ray diffraction and electron microscopy show the growth of interfacial Ti₃SiC₂. The as-deposited contacts are ohmic, in contrast to multistep processes with deposition followed by rapid thermal annealing. This procedure also offers the possibility of direct synthesis of oxygen-barrier capping layers before exposure to air, potentially improving contact stability in high-temperature and high-power devices.

Graphene-based chemical gas sensors normally show ultra-high sensitivity to certain gas molecules but at the same time suffer from poor selectivity and slow response and recovery Limes. Several approaches based on functionalization or modification of the graphene surface have been demonstrated as means to improve these issues, but most such measures result in poor reproducibility. In this study we investigate reproducible graphene surface modifications by sputter deposition of thin nanostructured Au or Pt layers. It is demonstrated that under the right metallization conditions the electronic properties of the surface remain those of graphene, while the surface chemistry is modified to improve sensitivity, selectivity and speed of response to nitrogen dioxide.

In this study, we use two different sensor technologies based on gas sensitive silicon carbide field effect transistors (SiC-FETs) and epitaxial graphene on SiC (EG/SiC) for highly sensitive and selective detection of trace amounts of three hazardous volatile organic compounds (VOCs), i.e. formaldehyde (CH₂O), benzene (C₆H₆), and naphthalene (C₁₀H₈), present in indoor environments in concentrations of health concern.

Iridium and platinum are used as sensing layers for the gate contacts. The FET sensors are operated at high temperature, under static and dynamic conditions. Excellent detection limits of 10 ppb for CH₂O, about 1 ppb for C₆H₆, and below 0.5 ppb for C₁₀H₈ are measured at 60 % relative humidity (r.h.) [1]. The selectivity of the sensors is increased by temperature cycled operation and data evaluation based on multivariate statistics. Discrimination of CH₂O, C₆H₆, and C₁₀H₈ independent of the level of background humidity is possible with a very high cross-validation rate up to 90 % [2]. These results are very encouraging for indoor air quality control, being below the threshold limits recommended by the WHO guidelines.

Graphene-based chemical sensors offer the advantage of extreme sensitivity due to graphene’s unique electronic properties and the fact that every single atom is at the surface and available to interact with gas molecules. For this reason, uniform monolayer graphene is crucial [3], which is guaranteed by our optimized epitaxial growth process. Graphene-based chemical gas sensors normally show ultra-high sensitivity to certain gas molecules but suffer from poor selectivity. Functionalization or modification of the graphene surface can improve selectivity, but most such measures result in poor reproducibility. We demonstrate reproducible, non-destructive means of graphene surface decoration with nanostructured metals and metal oxides, and study their effect on the gas interactions at the graphene surface.

Gas sensitive silicon carbide field effect transistors with nanostructured Ir gate layershave been used for the first time for sensitive detection of volatile organic compounds (VOCs) atpart per billion level, for indoor air quality applications. Formaldehyde, naphthalene, and benzenehave been used as typical VOCs in dry air and under 10% and 20% relative humidity. A singleVOC was used at a time to study long-term stability, repeatability, temperature dependence, effectof relative humidity, sensitivity, response and recovery times of the sensors.

One of the main challenges in the fabrication of device quality graphene is the achievement of large area monolayer graphene that is processing compatible. Here, the impact of the substrate properties on the thickness uniformity and electronic characteristics for epitaxial graphene on SiC produced by high temperature sublimation has been evidenced and discussed. Several powerful techniques have been used to collect data, among them large scale ellipsometry mapping has been demonstrated for the first time. The study is covering all three SiC polytype, e.g. 4H-, 6H- and 3C-SiC in order to reveal eventual peculiarities that have to be controlled during graphene growth. The advantage of the cubic polytype is unambiguously demonstrated.

Using environmental scanning Kelvin probe microscopy we show that the position of the Fermi level of single layer graphene is more sensitive to chemical gating than that of double layer graphene. We calculate that the difference in sensitivity to chemical gating is not entirely due to the difference in band structure of 1 and 2 layer graphene. The findings are important for gas sensing where the sensitivity of the electronic properties to gas adsorption are monitored and suggest that single layer graphene could make a more sensitive gas sensor than double layer graphene. We propose that the difference in surface potential between adsorbate-free single and double layer graphene, measured using scanning kelvin probe microscopy, can be used as a non-invasive method of estimating substrate-induced doping in epitaxial graphene.