Photoelectrochemical Solution Gated Graphene Field-Effect Transistor Functionalized by Enzymatic Cascade Reaction for Organophosphate Detection.

Solution Gated Graphene Field-Effect Transistors (SGGT) are eagerly anticipated as an amplification platform for fabricating advanced ultra-sensitive sensors, allowing significant modulation of the drain current with minimal gate voltage. However, few studies have focused on light-matter interplay gating control for SGGT. Herein, this challenge is addressed by creating an innovative photoelectrochemical solution-gated graphene field-effect transistor (PEC-SGGT) functionalized with enzyme cascade reactions (ECR) for Organophosphorus (OPs) detection. The ECR system, consisting of acetylcholinesterase (AChE) and CuBTC nanomimetic enzymes, selectively recognizes OPs and forms o-phenylenediamine (oPD) oligomers sediment on the PEC electrode, with layer thickness related to the OPs concentration, demonstrating time-integrated amplification. Under light stimulation, the additional photovoltage generated on the PEC gate electrode is influenced by the oPD oligomers sediment layer, creating a differentiated voltage distribution along the gate path. PEC-SGGT, inherently equipped with built-in amplification circuits, sensitively captures gate voltage changes and delivers output with an impressive thousandfold current gain. The seamless integration of these three amplification modes in this advanced sensor allows a good linear range and highly sensitive detection of OPs, with a detection limit as low as 0.05 pm. This work provides a proof-of-concept for the feasibility of light-assisted functionalized gate-controlled PEC-SGGT for small molecule detection.

Twisted Bilayer Graphene Induced by Intercalation.

Twisted bilayer graphene (tBLG) has gained significant attention due to its unique physical and electronic properties. However, efficient fabrication of high-quality tBLG with diverse twist angles is crucial to expedite research on angle-dependent physics and potential applications. In this study, an intercalation strategy utilizing organic molecules, such as 1,2-dichloroethane, is developed to weaken the interlayer interaction and induce slide or rotation of the topmost graphene layer for tBLG fabrication. The proportion of tBLGs in the resulting 1,2-dichloroethane-treated BLG (dtBLG) reaches up to 84.4% for twist angles ranging from 0° to 30°, surpassing previously reported methods using chemical vapor deposition (CVD). Moreover, the twist angle distribution is not uniform and tends to concentrate in the ranges of 0-10° and 20-30°. This facile and rapid intercalation-based methodology provides a practical solution for studying angle-dependent physics and advancing the utilization of twisted two-dimensional materials.

Amplification-Free Detection of SARS-CoV-2 and Respiratory Syncytial Virus Using CRISPR Cas13a and Graphene Field-Effect Transistors.

The clustered regularly interspaced short palindromic repeats (CRISPR)/CRISPR-associated (Cas) systems have recently received notable attention for their applications in nucleic acid detection. Despite many attempts, the majority of current CRISPR-based biosensors in infectious respiratory disease diagnostic applications still require target preamplifications. This study reports a new biosensor for amplification-free nucleic acid detection via harnessing the trans-cleavage mechanism of Cas13a and ultrasensitive graphene field-effect transistors (gFETs). CRISPR Cas13a-gFET achieves the detection of SARS-CoV-2 and respiratory syncytial virus (RSV) genome down to 1 attomolar without target preamplifications. Additionally, we validate the detection performance using clinical SARS-CoV-2 samples, including those with low viral loads (Ct value >30). Overall, these findings establish our CRISPR Cas13a-gFET among the most sensitive amplification-free nucleic acid diagnostic platforms to date.

Drift Suppression of Solution-Gated Graphene Field-Effect Transistors by Cation Doping for Sensing Platforms.

Solution-gated graphene field-effect transistors (SG-GFETs) provide an ideal platform for sensing biomolecules owing to their high electron/hole mobilities and 2D nature. However, the transfer curve often drifts in an electrolyte solution during measurements, making it difficult to accurately estimate the analyte concentration. One possible reason for this drift is that p-doping of GFETs is gradually countered by cations in the solution, because the cations can permeate into the polymer residue and/or between graphene and SiO2 substrates. Therefore, we propose doping sufficient cations to counter p-doping of GFETs prior to the measurements. For the pre-treatment, GFETs were immersed in a 15 mM sodium chloride aqueous solution for 25 h. The pretreated GFETs showed that the charge neutrality point (CNP) drifted by less than 3 mV during 1 h of measurement in a phosphate buffer, while the non-treated GFETs showed that the CNP was severely drifted by approximately 50 mV, demonstrating a 96% reduction of the drift by the pre-treatment. X-ray photoelectron spectroscopy analysis revealed the accumulation of sodium ions in the GFETs through pre-treatment. Our method is useful for suppressing drift, thus allowing accurate estimation of the target analyte concentration.

Polar Organic Gate Dielectrics for Graphene Field-Effect Transistor-Based Sensor Technology.

We have pioneered the use of liquid polar organic molecules as alternatives to rigid gate-dielectrics for the fabrication of graphene field-effect transistors. The unique high net dipole moment of various polar organic molecules allows for easy manipulation of graphene's conductivity due to the formation of an electrical double layer with a high-capacitance at the liquid and graphene interface. Here, we compare the performances of dimethyl sulfoxide (DMSO), acetonitrile, propionamide, and valeramide as polar organic liquid dielectrics in graphene field-effect transistors (GFETs). We demonstrate improved performance for a GFET with a liquid dielectric comprised of DMSO with high electron and hole mobilities of 154.0 cm²/Vs and 154.6 cm²/Vs, respectively, and a Dirac voltage <5 V.

Antenna-integrated 0.6 THz FET direct detectors based on CVD graphene.

We present terahertz (THz) detectors based on top-gated graphene field effect transistors (GFETs) with integrated split bow-tie antennas. The GFETs were fabricated using graphene grown by chemical vapor deposition (CVD). The THz detectors are capable of room-temperature rectification of a 0.6 THz signal and achieve a maximum optical responsivity better than 14 V/W and minimum optical noise-equivalent power (NEP) of 515 pW/Hz(0.5). Our results are a significant improvement over previous work on graphene direct detectors and are comparable to other established direct detector technologies. This is the first time room-temperature direct detection has been demonstrated using CVD graphene, which introduces the potential for scalable, wafer-level production of graphene detectors.

Graphene Sensor Arrays for Rapid and Accurate Detection of Pancreatic Cancer Exosomes in Patients' Blood Plasma Samples.

Biosensors based on graphene field effect transistors (GFETs) have the potential to enable the development of point-of-care diagnostic tools for early stage disease detection. However, issues with reproducibility and manufacturing yields of graphene sensors, but also with Debye screening and unwanted detection of nonspecific species, have prevented the wider clinical use of graphene technology. Here, we demonstrate that our wafer-scalable GFETs array platform enables meaningful clinical results. As a case study of high clinical relevance, we demonstrate an accurate and robust portable GFET array biosensor platform for the detection of pancreatic ductal adenocarcinoma (PDAC) in patients' plasma through specific exosomes (GPC-1 expression) within 45 min. In order to facilitate reproducible detection in blood plasma, we optimized the analytical performance of GFET biosensors via the application of an internal control channel and the development of an optimized test protocol. Based on samples from 18 PDAC patients and 8 healthy controls, the GFET biosensor arrays could accurately discriminate between the two groups while being able to detect early cancer stages including stages 1 and 2. Furthermore, we confirmed the higher expression of GPC-1 and found that the concentration in PDAC plasma was on average more than 1 order of magnitude higher than in healthy samples. We found that these characteristics of GPC-1 cancerous exosomes are responsible for an increase in the number of target exosomes on the surface of graphene, leading to an improved signal response of the GFET biosensors. This GFET biosensor platform holds great promise for the development of an accurate tool for the rapid diagnosis of pancreatic cancer.

Experimental comparison of direct and indirect aptamer-based biochemical functionalization of electrolyte-gated graphene field-effect transistors for biosensing applications.

Aptamer-based electrolyte-gated graphene field-effect transistor (EGFET) biosensors have gained considerable attention because of their rapidity and accuracy in terms of quantification of a wide range of biomarkers. Functionalization of the graphene channel of EGFETs with aptamer biorecognition elements (BREs) is a crucial step in fabrication of EGFET aptasensors. This paper presents a comprehensive comparison of commonly used biochemical functionalization approaches applied for preparation of sensing films in EGFET aptasensors, namely indirect and direct immobilization of BREs. This study is the first of its kind to experimentally compare the two BREs immobilization approaches in terms of their effects on the carrier mobility of the monolayer graphene channel and their suitability for sensing applications. Both approaches can preserve and even improve the carrier mobility of bare graphene channel and hence the sensitivity of the EGFET; however, the direct BREs immobilization method was selected to develop an aptameric EGFET biosensor as this method enables simpler and more efficient preparation of the graphene-based aptameric sensing film. The utility of the prepared EGFET aptasensor is demonstrated through detection of tumor necrosis factor-α (TNF-α), an important inflammatory biomarker. The direct BREs immobilization approach is applied to develop an EGFET aptasensor to measure TNF-α in a detection range from 10 pg/ml to 10 ng/ml, representative of its physiological level in human sweat, as a non-invasively accessible biofluid. The outstanding sensing performance of the developed TNF-α EGFET aptasensor based on direct BREs immobilization can pave the way for development of graphene biosensors.

2D Electronics Based on Graphene Field Effect Transistors: Tutorial for Modelling and Simulation.

This paper provides modeling and simulation insights into field-effect transistors based on graphene (GFET), focusing on the devices' architecture with regards to the position of the gate (top-gated graphene transistors, back-gated graphene transistors, and top-/back-gated graphene transistors), substrate (silicon, silicon carbide, and quartz/glass), and the graphene growth (CVD, CVD on SiC, and mechanical exfoliation). These aspects are explored and discussed in order to facilitate the selection of the appropriate topology for system-level design, based on the most common topologies. Since most of the GFET models reported in the literature are complex and hard to understand, a model of a GFET was implemented and made available in MATLAB, Verilog in Cadence, and VHDL-AMS in Simplorer-useful tools for circuit designers with different backgrounds. A tutorial is presented, enabling the researchers to easily implement the model to predict the performance of their devices. In short, this paper aims to provide the initial knowledge and tools for researchers willing to use GFETs in their designs at the system level, who are looking to implement an initial setup that allows the inclusion of the performance of GFETs.

A Sensitivity-Enhanced Electrolyte-Gated Graphene Field-Effect Transistor Biosensor by Acoustic Tweezers.

Low-abundance biomolecule detection is very crucial in many biological and medical applications. In this paper, we present a novel electrolyte-gated graphene field-effect transistor (EGFET) biosensor consisting of acoustic tweezers to increase the sensitivity. The acoustic tweezers are based on a high-frequency bulk acoustic resonator with thousands of MHz, which has excellent ability to concentrate nanoparticles. The operating principle of the acoustic tweezers to concentrate biomolecules is analyzed and verified by experiments. After the actuation of acoustic tweezers for 10 min, the IgG molecules are accumulated onto the graphene. The sensitivities of the EGFET biosensor with accumulation and without accumulation are compared. As a result, the sensitivity of the graphene-based biosensor is remarkably increased using SMR as the biomolecule concentrator. Since the device has advantages such as miniaturized size, low reagent consumption, high sensitivity, and rapid detection, we expect it to be readily applied to many biological and medical applications.

Atomic Layer Deposition of Layered Boron Nitride for Large-Area 2D Electronics.

Hexagonal boron nitride (h-BN) has been considered a promising dielectric for two-dimensional (2D) material-based electronics due to its atomically smooth and charge-free interface with an in-plane lattice constant similar to that of graphene. Here, we report atomic layer deposition of boron nitride (ALD-BN) using BCl3 and NH3 precursors directly on thermal SiO2 substrates at a relatively low temperature of 600 °C. The films were characterized by X-ray photoelectron spectroscopy, atomic force microscopy, and transmission electron microscopy wherein the uniform, atomically smooth, and nanocrystalline layered-BN thin film growth is observed. The growth rate is ∼0.042 nm/cycle at 600 °C, a temperature significantly lower than that of h-BN grown by chemical vapor deposition. The dielectric properties of the ALD-BN measured from Metal Oxide Semiconductor Capacitors are comparable with that of SiO2. Moreover, the ALD-BN exhibits a 2-fold increase in carrier mobility of graphene field effect transistors (G-FETs/ALD-BN/SiO2) due to the lower surface charge density and inert surface of ALD-BN in comparison to that of G-FETs fabricated on bare SiO2. Therefore, this work suggests that the transfer-free deposition of ALD-BN on SiO2 may be a promising candidate as a substrate for high performance graphene devices.

Electronic biosensors based on graphene FETs.

Olfaction is capable of accomplishing incredible tasks: it starts with capturing an odor molecule, delivering it to the odorant receptors, converting it into an electrical stimulus and transmitting the data to the brain. And all of this in milliseconds. The sense of smell is not yet fully decoded and is far from being replicated by modern sensor technologies. One approach to convert biological recognition- and binding events in real-time and in a label-free manner to electrical signals is emulated in a "biomimetic electronic smell sensor". It is based on a transistor, in many cases realized as a field-effect transistor (FET) with a biorecognition element, e.g., an odorant binding protein (OBP) converting the binding event of one of its typically many ligands directly into a measurable electrical signal. OBPs are immobilized on these FETs and modulate the current in the presence of smell molecules due to the charge redistribution in the gated channel. Graphene is an elegant candidate to realize such a sensor device because an atomic monolayer of a semiconducting material leads to increased sensitivity. Beside the direct molecule interaction with the substrate upon binding and its excellent biocompatible character, graphene has the advantage of a biological-friendly working point in the sub-Volt regime. Different approaches of preparation and functionalization of graphene field-effect transistors (gFETs) are utilized to tune the performance for odorant sensing. The evaluation of kinetic binding parameters like association and dissociation rate constants and the equilibrium affinity constants of protein-ligand interactions can be derived from the direct electrical read-out of such miniaturized sensor systems. In this article, the state of the art of gFET preparation, functionalization, and operation for odorant sensing will be discussed.

Low-Power Complementary Logic Circuit Using Polymer-Electrolyte-Gated Graphene Switching Devices.

The modulation of the electrical properties of graphene and its device configurations for low-power consumption are important in developing graphene-based logic electronics. Here, we demonstrate the change in the charge transport in graphene from ambipolar to unipolar using surface charge transfer doping of the polymer electrolyte. Unipolar graphene field-effect transistors (GFETs) were obtained by the surface treatment of poly(acrylic acid) (PAA) for p-type and poly(ethyleneimine) (PEI) for n-type as polymer-electrolyte gates. In addition, lithium perchlorate (LiClO4) in a polymer matrix can be used for the low-gate voltage operation of GFETs (less than ±3 V) because of its high gating efficiency. Using polymer-electrolyte-gated GFETs, complementary graphene inverters were fabricated with a voltage swing of 57% and maximum voltage gain (Vgain) of 1.1 at a low supply voltage (VDD = 1 V). This is expected to facilitate the development of graphene-based logic devices with low-cost, low-power, and flexible electronics.

van der Waals Contact Engineering of Graphene Field-Effect Transistors for Large-Area Flexible Electronics.

Graphene has great potential for high-performance flexible electronics. Although studied for more than a decade, contacting graphene efficiently, especially for large-area, flexible electronics, is still a challenge. Here, by engineering the graphene-metal van der Waals (vdW) contact, we demonstrate that ultralow contact resistance is achievable via a bottom-contact strategy incorporating a simple transfer process without any harsh thermal treatment (>150 °C). The majority of the fabricated devices show contact resistances below 200 Ω·µm with values as low as 65 Ω·µm achievable. This is on par with the state-of-the-art top- and edge-contacted graphene field-effect transistors. Further, our study reveals that these contacts, despite the presumed weak nature of the vdW interaction, are stable under various bending conditions, thus guaranteeing compatibility with flexible electronics with improved performance. This work illustrates the potential of the previously underestimated vdW contact approach for large-area flexible electronics.

Graphene Tribotronics for Electronic Skin and Touch Screen Applications.

Graphene tribotronics is introduced for touch-sensing applications such as electronic skins and touch screens. The devices are based on a coplanar coupling of triboelectrification and current transport in graphene transistors. The touch sensors are ultrasensitive, fast, and stable. Furthermore, they are transparent and flexible, and can spatially map touch stimuli such as movement of a ball, multi-touch, etc.

Graphene-based field effect transistor in two-dimensional paper networks.

We demonstrate the fabrication of a graphene-based field effect transistor (GFET) incorporated in a two-dimensional paper network format (2DPNs). Paper serves as both a gate dielectric and an easy-to-fabricate vessel for holding the solution with the target molecules in question. The choice of paper enables a simpler alternative approach to the construction of a GFET device. The fabricated device is shown to behave similarly to a solution-gated GFET device with electron and hole mobilities of ∼1256 cm(2) V(-1) s(-1) and ∼2298 cm(2) V(-1) s(-1) respectively and a Dirac point around ∼1 V. When using solutions of ssDNA and glucose it was found that the added molecules induce negative electrolytic gating effects shifting the conductance minimum to the right, concurrent with increasing carrier concentrations which results to an observed increase in current response correlated to the concentration of the solution used.