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Iridium and ruthenium and their oxides/hydroxides are the best candidates for the oxygen evolution reaction under harsh acidic conditions owing to the low overpotentials observed for Ru- and Ir-based anodes and the high corrosion resistance of Ir-oxides. Herein, by means of cutting edge operando surface and bulk sensitive X-ray spectroscopy techniques, specifically designed electrode nanofabrication and ab initio DFT calculations, we were able to reveal the electronic structure of the active IrOx centers (i.e., oxidation state) during electrocatalytic oxidation of water in the surface and bulk of high-performance Ir-based catalysts. We found the oxygen evolution reaction is controlled by the formation of empty Ir 5d states in the surface ascribed to the formation of formally IrV species leading to the appearance of electron-deficient oxygen species bound to single iridium atoms (µ1-O and µ1-OH) that are responsible for water activation and oxidation. Oxygen bound to three iridium centers (µ3-O) remains the dominant species in the bulk but do not participate directly in the electrocatalytic reaction, suggesting bulk oxidation is limited. In addition a high coverage of a µ1-OO (peroxo) species during the OER is excluded. Moreover, we provide the first photoelectron spectroscopic evidence in bulk electrolyte that the higher surface-to-bulk ratio in thinner electrodes enhances the material usage involving the precipitation of a significant part of the electrode surface and near-surface active species.
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The discovery of the field effect in graphene initiated the development of graphene field effect transistor (FET) sensors, wherein high mobility surface conduction is readily modulated by surface adsorption. For all graphene transistor sensors, low-frequency 1/f noise determines sensor resolution, and the absolute measure of 1/f noise is thus a crucial performance metric for sensor applications. Here we report a simple method for reducing 1/f noise by scaling the active area of graphene FET sensors. We measured 1/f noise in graphene FETs with size 5 µm × 5 µm to 5.12 mm × 5.12 mm, observing more than five orders of magnitude reduction in 1/f noise. We report the lowest normalized graphene 1/f noise parameter observed to date, 5 × 10-13, and we demonstrate a sulfate ion sensor with a record resolution of 1.2 × 10-3 log molar concentration units. Our work highlights the importance of area scaling in graphene FET sensor design, wherein increased channel area improves sensor resolution.
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The superior intrinsic mechanical properties of graphene have been widely studied and utilized to enhance the mechanical properties of various composite materials. However, it is still unclear how heterostructures incorporating graphene behave, and to what extent graphene influences their mechanical response. In this work, a series of graphene/Al2O3 composite films were fabricated via atomic layer deposition of Al2O3 on graphene, and their mechanical behavior was studied using an experimental-computational approach. The inclusion of monolayer chemical vapor deposited graphene between ultrathin Al2O3 films (1.5-4.5 nm thickness) was found to enhance the overall stiffness by as much as 70% compared to a pure Al2O3 film of similar thickness (â¼150 GPa to â¼250 GPa). Here, for the first time, the combination of graphene and Al2O3 in vertically-stacked heterostructures results in advanced hybrid films of unprecedented mechanical stiffness that also possess qualities desirable for graphene-based transistors and flexible electronics.
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The ability to manipulate optical fields and the energy flow of light is central to modern information and communication technologies, as well as quantum information processing schemes. However, because photons do not possess charge, a way of controlling them efficiently by electrical means has so far proved elusive. A promising way to achieve electric control of light could be through plasmon polaritonscoupled excitations of photons and charge carriersin graphene. In this two-dimensional sheet of carbon atoms, it is expected that plasmon polaritons and their associated optical fields can readily be tuned electrically by varying the graphene carrier density. Although evidence of optical graphene plasmon resonances has recently been obtained spectroscopically, no experiments so far have directly resolved propagating plasmons in real space. Here we launch and detect propagating optical plasmons in tapered graphene nanostructures using near-field scattering microscopy with infrared excitation light. We provide real-space images of plasmon fields, and find that the extracted plasmon wavelength is very shortmore than 40 times smaller than the wavelength of illumination. We exploit this strong optical field confinement to turn a graphene nanostructure into a tunable resonant plasmonic cavity with extremely small mode volume. The cavity resonance is controlled in situ by gating the graphene, and in particular, complete switching on and off of the plasmon modes is demonstrated, thus paving the way towards graphene-based optical transistors. This successful alliance between nanoelectronics and nano-optics enables the development of active subwavelength-scale optics and a plethora of nano-optoelectronic devices and functionalities, such as tunable metamaterials, nanoscale optical processing, and strongly enhanced lightmatter interactions for quantum devices and biosensing applications.
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Graphene has extraordinary mechanical and electronic properties, making it a promising material for membrane-based nanoelectromechanical systems (NEMS). Here, chemical-vapor-deposited graphene is transferred onto target substrates to suspend it over cavities and trenches for pressure-sensor applications. The development of such devices requires suitable metrology methods, i.e., large-scale characterization techniques, to confirm and analyze successful graphene transfer with intact suspended graphene membranes. We propose fast and noninvasive Raman spectroscopy mapping to distinguish between free-standing and substrate-supported graphene, utilizing the different strain and doping levels. The technique is expanded to combine two-dimensional area scans with cross-sectional Raman spectroscopy, resulting in three-dimensional Raman tomography of membrane-based graphene NEMS. The potential of Raman tomography for in-line monitoring is further demonstrated with a methodology for automated data analysis to spatially resolve the material composition in micrometer-scale integrated devices, including free-standing and substrate-supported graphene. Raman tomography may be applied to devices composed of other two-dimensional materials as well as silicon micro- and nanoelectromechanical systems.
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Previous statistical studies on the mechanical properties of chemical-vapor-deposited (CVD) suspended graphene membranes have been performed by means of measuring individual devices or with techniques that affect the material. Here, we present a colorimetry technique as a parallel, noninvasive, and affordable way of characterizing suspended graphene devices. We exploit Newton's rings interference patterns to study the deformation of a double-layer graphene drum 13.2 µm in diameter when a pressure step is applied. By studying the time evolution of the deformation, we find that filling the drum cavity with air is 2-5 times slower than when it is purged.
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The remarkable properties of graphene, such as broadband optical absorption, high carrier mobility, and short photogenerated carrier lifetime, are particularly attractive for high-frequency optoelectronic devices operating at 1.55 µm telecom wavelength. Moreover, the possibility to transfer graphene on a silicon substrate using a complementary metal-oxide-semiconductor-compatible process opens the ability to integrate electronics and optics on a single cost-effective chip. Here, we report an optoelectronic mixer based on chemical vapor-deposited graphene transferred on an oxidized silicon substrate. Our device consists in a coplanar waveguide that integrates a graphene channel, passivated with an atomic layer-deposited Al2O3 film. With this new structure, 30 GHz optoelectronic mixing in commercially available graphene is demonstrated for the first time. In particular, using a 30 GHz intensity-modulated optical signal and a 29.9 GHz electrical signal, we show frequency downconversion to 100 MHz. These results open promising perspectives in the domain of optoelectronics for radar and radio-communication systems.
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We demonstrate wafer-scale, non-contact mapping of essential carrier transport parameters, carrier mobility (µdrift), carrier density (Ns), DC sheet conductance (σdc), and carrier scattering time (τsc) in CVD graphene, using spatially resolved terahertz time-domain conductance spectroscopy. σdc and τsc are directly extracted from Drude model fits to terahertz conductance spectra obtained in each pixel of 10 × 10 cm2 maps with a 400 µm step size. σdc- and τsc-maps are translated into µdrift and Ns maps through Boltzmann transport theory for graphene charge carriers and these parameters are directly compared to van der Pauw device measurements on the same wafer. The technique is compatible with all substrate materials that exhibit a reasonably low absorption coefficient for terahertz radiation. This includes many materials used for transferring CVD graphene in production facilities as well as in envisioned products, such as polymer films, glass substrates, cloth, or paper substrates.
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Fabricating stable functional devices at the atomic scale is an ultimate goal of nanotechnology. In biological processes, such high-precision operations are accomplished by enzymes. A counterpart molecular catalyst that binds to a solid-state substrate would be highly desirable. Here, we report the direct observation of single Si adatoms catalyzing the dissociation of carbon atoms from graphene in an aberration-corrected high-resolution transmission electron microscope (HRTEM). The single Si atom provides a catalytic wedge for energetic electrons to chisel off the graphene lattice, atom by atom, while the Si atom itself is not consumed. The products of the chiseling process are atomic-scale features including graphene pores and clean edges. Our experimental observations and first-principles calculations demonstrated the dynamics, stability, and selectivity of such a single-atom chisel, which opens up the possibility of fabricating certain stable molecular devices by precise modification of materials at the atomic scale.
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Grafite/química , Modelos Químicos , Impressão Molecular/métodos , Nanopartículas/química , Nanopartículas/ultraestrutura , Silício/química , Catálise , Simulação por Computador , Teste de Materiais , Microscopia Eletrônica/métodos , Modelos Moleculares , Propriedades de SuperfícieRESUMO
The reliability of analysis is becoming increasingly important as point-of-care diagnostics are transitioning from single-analyte detection toward multiplexed multianalyte detection. Multianalyte detection benefits greatly from complementary metal-oxide semiconductor (CMOS) integrated sensing solutions, offering miniaturized multiplexed sensing arrays with integrated readout electronics and extremely large sensor counts. The development of CMOS back end of line integration compatible graphene field-effect transistor (GFET)-based biosensing has been rapid during the past few years, in terms of both the fabrication scale-up and functionalization toward biorecognition from real sample matrices. The next steps in industrialization relate to improving reliability and require increased statistics. Regarding functionalization toward truly quantitative sensors, on-chip bioassays with improved statistics require sensor arrays with reduced variability in functionalization. Such multiplexed bioassays, whether based on graphene or on other sensitive nanomaterials, are among the most promising technologies for label-free electrical biosensing. As an important step toward that, we report wafer-scale fabrication of CMOS-integrated GFET arrays with high yield and uniformity, designed especially for biosensing applications. We demonstrate the operation of the sensing platform array with 512 GFETs in simultaneous detection for the sodium chloride concentration series. This platform offers a truly statistical approach on GFET-based biosensing and further to quantitative and multianalyte sensing. The reported techniques can also be applied to other fields relying on functionalized GFETs, such as gas or chemical sensing or infrared imaging.
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COVID-19, caused by the severe acute respiratory syndrome-coronavirus 2 (SARS-CoV-2), originated a global health crisis, causing over 2 million casualties and altering human daily life all over the world. This pandemic emergency revealed the limitations of current diagnostic tests, highlighting the urgency to develop faster, more precise and sensitive sensors. Graphene field effect transistors (GFET) are analytical platforms that enclose all these requirements. However, the design of a sensitive and robust GFET is not a straightforward objective. In this work, we report a GFET array biosensor for the detection of SARS-CoV-2 spike protein using the human membrane protein involved in the virus internalisation: angiotensin-converting enzyme 2 (ACE2). By finely controlling the graphene functionalisation, by tuning the Debye length, and by deeply characterising the ACE2-spike protein interactions, we have been able to detect the target protein with an extremely low limit of detection (2.94 aM). This work set the basis for a new class of analytical platforms, based on human membrane proteins, with the potential to detect a broad variety of pathogens, even before their isolation, being a powerful tool in the fight against future pandemics.
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COVID-19 , Grafite , Humanos , COVID-19/diagnóstico , SARS-CoV-2 , Glicoproteína da Espícula de Coronavírus/metabolismo , Enzima de Conversão de Angiotensina 2/metabolismo , Ligação ProteicaRESUMO
In this work, we report a novel method of label-free detection of small molecules based on direct observation of interferometric signal change in graphene-modified glasses. The interferometric sensor chips are fabricated via a conventional wet transfer method of CVD-grown graphene onto the glass coverslips, lowering the device cost and allowing for upscaling the sensor fabrication. For the first time, we report the use of graphene functionalized by the aptamer as the bioreceptor, in conjunction with Spectral-Phase Interferometry (SPI) for detection of ochratoxin A (OTA). In a direct assay with an OTA-specific aptamer, we demonstrated a quick and significant change of the optical signal in response to the maximum tolerable level of OTA concentration. The sensor regeneration is possible in urea solution. The developed platform enables a direct method of kinetic analysis of small molecules using a low-cost optical chip with a graphene-aptamer sensing layer.
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The choice of the right material is essential in microwave processing. The carbon materials are good microwave absorbers, which allows them to be transformed by microwave heating into new carbon materials with adapted properties, capable of heating other materials indirectly. In this paper, the microwave heating of graphene as reinforcement of the lithium aluminosilicate (LAS) ceramics has been explored. LAS ceramics have a near-zero coefficient of thermal expansion and exhibit an effective and efficient heating by microwave. Nevertheless, we have found that the graphene did not show any significant response to the microwave radiation and, hence, the interaction as mechanical reinforcement with the LAS material is harmful. The possible benefits of graphene materials to microwave technology are widely known; however, the mechanism involved in the interaction of microwave radiation with ceramic-graphene composites with high dielectric loss factors has not been addressed earlier.
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Real-time, high resolution, simultaneous measurement of multiple ionic species is challenging with existing chromatographic, spectrophotometric and potentiometric techniques. Potentiometric ion sensors exhibit limitations in both resolution and selectivity. Herein, we develop wafer scale graphene transistor technology for overcoming these limitations. Large area graphene is an ideal material for high resolution ion sensitive field effect transistors (ISFETs), while simultaneously enabling facile fabrication as compared to conventional semiconductors. We develop the ISFETs into an array and apply Nikolskii-Eisenman analysis to account for cross-sensitivity and thereby achieve high selectivity. We experimentally demonstrate real-time, simultaneous concentration measurement of K+, Na+, [Formula: see text], [Formula: see text], [Formula: see text], [Formula: see text] and Cl- with a resolution of [Formula: see text] concentration units. The array achieves an accuracy of ±0.05 log concentration. Finally, we demonstrate real-time ion concentration measurement in an aquarium with lemnoideae lemna over three weeks, where mineral uptake by aquatic organisms can be observed during their growth.
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Grafite/química , Eletrodos Seletivos de Íons , Transistores Eletrônicos , Ânions , Cátions , Eletrólitos/química , Concentração de Íons de Hidrogênio , Imagem Óptica , Temperatura , Fatores de TempoRESUMO
Besides inhalation, skin contact may be considered one of the most relevant exposure routes to graphene-based materials (GBMs). However, very few data on the cutaneous toxicity of these materials are available, so far. This study is focused on skin irritation potential of a panel of GBMs: few-layer graphene (FLG), exfoliated by ball milling of graphite, FLG exfoliated by ultrasonication using sodium dodecyl sulfate (FLG-SDS) or sodium dodecylbenzenesulfonate (FLG-SDBS), CVD-graphene, obtained by chemical vapor deposition, graphene oxide (GO) and reduced GO (rGO). Skin irritation was assessed using the SkinEthic™ Reconstructed human Epidermis (RhE), following the Organisation for Economic Co-operation and Development (OECD) Test Guideline (TG) 439. Even though not validated for nanomaterials, the OCED TG 439 turned out to be applicable also for GBM testing, since no interference with the methylthiazolyldiphenyl-tetrazolium bromide (MTT) reduction, used as a final readout, was found. Furthermore, direct epidermal exposure to powdered GBMs mimics the actual human exposure, avoiding interference by the cell culture medium (protein corona formation). Only GBMs prepared with irritant surfactants (FLG-SDS and FLG-SDBS), but not the others, reduced RhE viability at levels lower than those predicting skin irritation (≤50%), suggesting irritant properties. This result was further confirmed by measuring cytokine (IL-1α, IL-6 and IL-8) release by GBM-treated RhE and by histological analysis as additional readouts to implement the guideline. On the whole, these results demonstrate that GBMs prepared with non-irritant exfoliation agents do not induce skin irritation after a single acute exposure.
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Alternativas aos Testes com Animais , Grafite/toxicidade , Nanoestruturas/toxicidade , Testes de Irritação da Pele , Citocinas/metabolismo , Epiderme/efeitos dos fármacos , Epiderme/metabolismo , Proteínas Filagrinas , Grafite/química , Humanos , Modelos Biológicos , Nanoestruturas/química , Tensoativos/química , Tensoativos/toxicidadeRESUMO
Graphene has become the focus of extensive research efforts and it can now be produced in wafer-scale. For the development of next generation graphene-based electronic components, electrical characterization of graphene is imperative and requires the measurement of work function, sheet resistance, carrier concentration and mobility in both macro-, micro- and nano-scale. Moreover, commercial applications of graphene require fast and large-area mapping of electrical properties, rather than obtaining a single point value, which should be ideally achieved by a contactless measurement technique. We demonstrate a comprehensive methodology for measurements of the electrical properties of graphene that ranges from nano- to macro- scales, while balancing the acquisition time and maintaining the robust quality control and reproducibility between contact and contactless methods. The electrical characterisation is achieved by using a combination of techniques, including magneto-transport in the van der Pauw geometry, THz time-domain spectroscopy mapping and calibrated Kelvin probe force microscopy. The results exhibit excellent agreement between the different techniques. Moreover, we highlight the need for standardized electrical measurements in highly controlled environmental conditions and the application of appropriate weighting functions.
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Electronic applications of large-area graphene films require rapid and accurate methods to map their electrical properties. Here we present the first electrical resistance tomography (ERT) measurements on large-area graphene samples, obtained with a dedicated measurement setup and reconstruction software. The outcome of an ERT measurement is a map of the graphene electrical conductivity. The same setup allows to perform van der Pauw (vdP) measurements of the average conductivity. We characterised the electrical conductivity of chemical-vapour deposited graphene samples by performing ERT, vdP and scanning terahertz time-domain spectroscopy (TDS), the last one by means of a commercial instrument. The measurement results are compared and discussed, showing the potential of ERT as an accurate and reliable technique for the electrical characterization of graphene samples.
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Electro-optic modulators based on micro-electromechanical systems have found success as elements for optical projectors, for simplified optical spectrometers, and as reflective-type screens that make use of light interference (Interferometric Modulator Display technology). The latter concept offers an exciting avenue for graphene nanomechanical structures to replace classical micro-electromechanical devices and bring about enhancement in performance, especially switching speed and voltage. In this work we study the optical response of electrically actuated graphene drumheads by means of spectrometric and stroboscopic experiments. The color reproducibility and speed of these membranes in producing the desired electro-optic modulation makes them suitable as pixels for high refresh rate displays. As a proof of concept, we demonstrate a Graphene Interferometric Modulator Display prototype with 5 µm-in-diameter pixels that compose a high resolution image (2500 pixels per inch)-equivalent to a 5â³ display of 12K-whose color can be changed at frame rates of at least 400 Hz.
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We describe the fabrication and characterisation of a capacitive pressure sensor formed by an ultra-thin graphene-polymer heterostructure membrane spanning a large array of micro-cavities each up to 30 µm in diameter with 100% yield. Sensors covering an area of just 1 mm2 show reproducible pressure transduction under static and dynamic loading up to pressures of 250 kPa. The measured capacitance change in response to pressure is in good agreement with calculations. Further, we demonstrate high-sensitivity pressure sensors by applying a novel strained membrane transfer and optimising the sensor architecture. This method enables suspended structures with less than 50 nm of air dielectric gap, giving a pressure sensitivity of 123 aF Pa-1 mm-2 over a pressure range of 0 to 100 kPa.
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We use a scalable optical technique to characterize more than 21 000 circular nanomechanical devices made of suspended single- and double-layer graphene on cavities with different diameters (D) and depths (g). To maximize the contrast between suspended and broken membranes we used a model for selecting the optimal color filter. The method enables parallel and automatized image processing for yield statistics. We find the survival probability to be correlated with a structural mechanics scaling parameter given by D4/g3. Moreover, we extract a median adhesion energy of Γ = 0.9 J m-2 between the membrane and the native SiO2 at the bottom of the cavities.