Electron-Tunneling Modulation in Percolating Network of Graphene Quantum Dots: Fabrication, Phenomenological Understanding, and Humidity/Pressure Sensing Applications

The two-dimensional (2D) electron cloud, flexible carbon carbon bonds, chemical modifiability, and size-dependent quantum confinement and capacitance makes graphene nanostructures (GN) a widely tunable material for electronics. Here we report the oxidation-led edge-roughening and cleavage of long graphene nanoribbons (GNRs) (150 nm wide) synthesized via nanotomy (nanoscale cutting) of graphite (with 2 nm edged diamond knife) to produce graphene quantum dots (GQD). These GQDs (similar to 100-200 nm) selectively interfaced with polyelectrolyte microfiber (diameter = 2-20 pm) form an electrically percolating-network exhibiting a characteristic Coulomb blockade signature with a dry tunneling distance of 0.58 nm and conduction activation energy of 3 meV. We implement this construct to demonstrate the functioning of humidity and pressure sensors and outline their governing model. Here, a 0.36 nm decrease in the average tunneling-barrier-width between GQDs (tunneling barrier = 5.11 eV) increases the conductivity of the device by 43-fold. These devices leverage the modulation in electron tunneling distances caused by pressure and humidity induced water transport across the hygroscopic polymer microfiber (Henry's constant = 0.215 Torr(-1)). This is the foremost example of GQD-based electronic sensors. We envision that this polymer-interfaced GQD percolating network will evolve a new class of sensors leveraging the low mass, low capacitance, high conductivity, and high sensitivity of GQD and the interfacial or dielectric properties of the polymer fiber.