Tunable Reverse‐Biased Graphene/Silicon Heterojunction Schottky Diode Sensor

A new chemical sensor based on reverse‐biased graphene/Si heterojunction diode has been developed that exhibits extremely high bias‐dependent molecular detection sensitivity and low operating power. The device takes advantage of graphene's atomically thin nature, which enables molecular adsorption on its surface to directly alter graphene/Si interface barrier height, thus affecting the junction current exponentially when operated in reverse bias and resulting in ultrahigh sensitivity. By operating the device in reverse bias, the work function of graphene, and hence the barrier height at the graphene/Si heterointerface, can be controlled by the bias magnitude, leading to a wide tunability of the molecular detection sensitivity. Such sensitivity control is also possible by carefully selecting the graphene/Si heterojunction Schottky barrier height. Compared to a conventional graphene amperometric sensor fabricated on the same chip, the proposed sensor demonstrated 13 times higher sensitivity for NO₂ and 3 times higher for NH₃ in ambient conditions, while consuming ～500 times less power for same magnitude of applied voltage bias. The sensing mechanism based on heterojunction Schottky barrier height change has been confirmed using capacitance‐voltage measurements.     

Molecule–Graphene Hybrid Materials with Tunable Mechanoresponse: Highly Sensitive Pressure Sensors for Health Monitoring

The development of pressure sensors is crucial for the implementation of electronic skins and for health monitoring integrated into novel wearable devices. Tremendous effort is devoted toward improving their sensitivity, e.g., by employing microstructured electrodes or active materials through cumbersome processes. Here, a radically new type of piezoresistive pressure sensor based on a millefeuille‐like architecture of reduced graphene oxide (rGO) intercalated by covalently tethered molecular pillars holding on‐demand mechanical properties are fabricated. By applying a tiny pressure to the multilayer structure, the electron tunnelling ruling the charge transport between successive rGO sheets yields a colossal decrease in the material's electrical resistance. Significantly, the intrinsic rigidity of the molecular pillars employed enables the fine‐tuning of the sensor's sensitivity, reaching sensitivities as high as 0.82 kPa^?1 in the low pressure region (0–0.6 kPa), with short response times (≈24 ms) and detection limit (7 Pa). The pressure sensors enable efficient heartbeat monitoring and can be easily transformed into a matrix capable of providing a 3D map of the pressure exerted by different objects.     

High‐Concentration Solvent Exfoliation of Graphene

A method is demonstrated to prepare graphene dispersions at high concentrations, up to 1.2 mg mL^?1, with yields of up to 4 wt% monolayers. This process relies on low‐power sonication for long times, up to 460 h. Transmission electron microscopy shows the sonication to reduce the flake size, with flake dimensions scaling as t^?1/2. However, the mean flake length remains above 1 µm for all sonication times studied. Raman spectroscopy shows defects are introduced by the sonication process. However, detailed analysis suggests that predominately edge, rather than basal‐plane, defects are introduced. These dispersions are used to prepare high‐quality free‐standing graphene films. The dispersions can be heavily diluted by water without sedimentation or aggregation. This method facilitates graphene processing for a range of applications.     

Graphene–Graphene Interactions: Friction,Superlubricity, and Exfoliation

Graphite's lubricating properties due to the “weak” interactions between individual layers have long been known. However, these interactions are not weak enough to allow graphite to readily exfoliate into graphene on a large scale. Separating graphite layers down to a single sheet is an intense area of research as scientists attempt to utilize graphene's superlative properties. The exfoliation and processing of layered materials is governed by the friction between layers. Friction on the macroscale can be intuitively understood, but there is little understanding of the mechanisms involved in nanolayered materials. Using molecular dynamics and a new forcefield, graphene's unusual behavior in a superlubric state is examined, and the energy dissipated between two such surfaces sliding past each other is shown. The dependence of friction on temperature and surface roughness is described, and agreement with experiment is reported. The accuracy of the simulated behavior enables the processes that drive exfoliation of graphite into individual graphene sheets to be described. Taking into account the friction between layers, a peeling mechanism of exfoliation is predicted to be of lower energy cost than shearing.     

A Supramolecular Strategy to Leverage the Liquid‐Phase Exfoliation of Graphene in the Presence of Surfactants: Unraveling the Role of the Length of Fatty Acids

Achieving the full control over the production as well as processability of high‐quality graphene represents a major challenge with potential interest in the field of fabrication of multifunctional devices. The outstanding effort dedicated to tackle this challenge in the last decade revealed that certain organic molecules are capable of leveraging the exfoliation of graphite with different efficiencies. Here, a fundamental understanding on a straightforward supramolecular approach for producing homogenous dispersions of unfunctionalized and non‐oxidized graphene nanosheets in four different solvents is attained, namely N‐methyl‐2‐pyrrolidinone, N,N‐dimethylformamide, ortho‐dichlorobenzene, and 1,2,4‐trichlorobenzene. In particular, a comparative study on the liquid‐phase exfoliation of graphene in the presence of linear alkanes of different lengths terminated by a carboxylic‐acid head group is performed. These molecules act as graphene dispersion‐stabilizing agents during the exfoliation process. The efficiency of the exfoliation in terms of concentration of exfoliated graphene is found to be proportional to the length of the employed fatty acid. Importantly, a high percentage of single‐layer graphene flakes is revealed by high‐resolution transmission electron microscopy and Raman spectroscopy analyses. A simple yet effective thermodynamic model is developed to interpret the chain‐length dependence of the exfoliation yield. This approach relying on the synergistic effect of a ad‐hoc solvent and molecules to promote the exfoliation of graphene in liquid media represents a promising and modular strategy towards the rational design of improved dispersion‐stabilizing agents.     

Electric‐Field‐Tunable Conductivity in Graphene/Water and Graphene/Ice Systems

This study demonstrates that the application of an external electrical potential to a phenyl‐sulfonic functionalized graphene (SG)/water suspension distinctly enhances its electrical conductivity via the structural transition from isolated clusters to a 3D SG network. Microstructural and alternating current impedance spectroscopy studies indicate that the surface charge plays an important role in the state of dispersion and connectivity of the SG in the suspension due to the potential‐dependent interactions with functional groups on the SG surface in the presence of an external electrical potential. In addition, the conductive SG/ice can be produced via liquid–solid phase transition of the SG/water suspension in the presence of an external electrical potential, which shows a one‐order magnitude improvement in electrical conductivity compared with pure ice. The electric‐field‐tunable property advances the understanding of nanofluid systems and has many potential applications.     

High Electrocatalytic and Wettable Nitrogen‐Doped Microwave‐Exfoliated Graphene Nanosheets as Counter Electrode for Dye‐Sensitized Solar Cells

In this paper, high electrocatalytic and wettable nitrogen‐doped microwave‐exfoliated graphene (N‐MEG) nanosheets are used as Pt‐free counter electrode (CE) for dye‐sensitized solar cells (DSSCs). A low cost solution‐based process is developed by using cyanamide (NH₂CN) at room temperature and normal pressure. The pyrrolic and pyridinic N atoms are doped into the carbon conjugated lattice to enhance electrocatalytic activity. N‐MEG film having N‐doping active sites and large porosity provides a wettable surface to facilitate electrolyte diffusion so that improves fill factor. Moreover, the control of the air exposure time after completing N‐MEG film is found to be crucial to obtain a reliable N‐MEG CE. A high DSSC efficiency up to 7.18% can be achieved based on N‐MEG CE, which is nearly comparable to conventional Pt CE.     

In Situ Exfoliated,Edge‐Rich,Oxygen‐Functionalized Graphene from Carbon Fibers for Oxygen Electrocatalysis

Metal‐free electrocatalysts have been extensively developed to replace noble metal Pt and RuO₂ catalysts for the oxygen reduction reaction (ORR) and oxygen evolution reaction (OER) in fuel cells or metal–air batteries. These electrocatalysts are usually deposited on a 3D conductive support (e.g., carbon paper or carbon cloth (CC)) to facilitate mass and electron transport. For practical applications, it is desirable to create in situ catalysts on the carbon fiber support to simplify the fabrication process for catalytic electrodes. In this study, the first example of in situ exfoliated, edge‐rich, oxygen‐functionalized graphene on the surface of carbon fibers using Ar plasma treatment is successfully prepared. Compared to pristine CC, the plasma‐etched carbon cloth (P‐CC) has a higher specific surface area and an increased number of active sites for OER and ORR. P‐CC also displays good intrinsic electron conductivity and excellent mass transport. Theoretical studies show that P‐CC has a low overpotential that is comparable to Pt‐based catalysts, as a result of both defects and oxygen doping. This study provides a simple and effective approach for producing highly active in situ catalysts on a carbon support for OER and ORR.