ABSTRACT

Graphene films grown on Cu foils have been fluorinated with xenon difluoride (XeF(2)) gas on one or both sides. When exposed on one side the F coverage saturates at 25% (C(4)F), which is optically transparent, over 6 orders of magnitude more resistive than graphene, and readily patterned. Density functional calculations for varying coverages indicate that a C(4)F configuration is lowest in energy and that the calculated band gap increases with increasing coverage, becoming 2.93 eV for one C(4)F configuration. During defluorination, we find hydrazine treatment effectively removes fluorine while retaining graphene's carbon skeleton. The same films may be fluorinated on both sides by transferring graphene to a silicon-on-insulator substrate enabling XeF(2) gas to etch the Si underlayer and fluorinate the backside of the graphene film to form perfluorographane (CF) for which calculated the band gap is 3.07 eV. Our results indicate single-side fluorination provides the necessary electronic and optical changes to be practical for graphene device applications.

Two-dimensional materials such as graphene show great potential for future nanoscale electronic devices. The high surface-to-volume ratio is a natural asset for applications such as chemical sensing, where perturbations to the surface resulting in charge redistribution are readily manifested in the transport characteristics. Here we show that single monolayer MoS(2) functions effectively as a chemical sensor, exhibiting highly selective reactivity to a range of analytes and providing sensitive transduction of transient surface physisorption events to the conductance of the monolayer channel. We find strong response upon exposure to triethylamine, a decomposition product of the V-series nerve gas agents. We discuss these results in the context of analyte/sensor interaction in which the analyte serves as either an electron donor or acceptor, producing a temporary charge perturbation of the sensor material. We find highly selective response to electron donors and little response to electron acceptors, consistent with the weak n-type character of our MoS(2). The MoS(2) sensor exhibits a much higher selectivity than carbon nanotube-based sensors.

We show that the capacitance of single-walled carbon nanotubes (SWNTs) is highly sensitive to a broad class of chemical vapors and that this transduction mechanism can form the basis for a fast, low-power sorption-based chemical sensor. In the presence of a dilute chemical vapor, molecular adsorbates are polarized by the fringing electric fields radiating from the surface of a SWNT electrode, which causes an increase in its capacitance. We use this effect to construct a high-performance chemical sensor by thinly coating the SWNTs with chemoselective materials that provide a large, class-specific gain to the capacitance response. Such SWNT chemicapacitors are fast, highly sensitive, and completely reversible.

We explore the electronic response of single-walled carbon nanotubes (SWNT) to trace levels of chemical vapors. We find adsorption at defect sites produces a large electronic response that dominates the SWNT capacitance and conductance sensitivity. This large response results from increased adsorbate binding energy and charge transfer at defect sites. Finally, we demonstrate controlled introduction of oxidation defects can be used to enhance sensitivity of a SWNT network sensor to a variety of chemical vapors.