Jeremy T. Robinson

Properties of Fluorinated Graphene Films

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 graphenes 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.

Manipulating Thermal Conductance at Metal−Graphene Contacts via Chemical Functionalization

Graphene-based devices have garnered tremendous attention due to the unique physical properties arising from this purely two-dimensional carbon sheet leading to tremendous efficiency in the transport of thermal carriers (i.e., phonons). However, it is necessary for this two-dimensional material to be able to efficiently transport heat into the surrounding 3D device architecture in order to fully capitalize on its intrinsic transport capabilities. Therefore, the thermal boundary conductance at graphene interfaces is a critical parameter in the realization of graphene electronics and thermal solutions. In this work, we examine the role of chemical functionalization on the thermal boundary conductance across metal/graphene interfaces. Specifically, we metalize graphene that has been plasma functionalized and then measure the thermal boundary conductance at Al/graphene/SiO(2) contacts with time domain thermoreflectance. The addition of adsorbates to the graphene surfaces are shown to influence the cross plane thermal conductance; this behavior is attributed to changes in the bonding between the metal and the graphene, as both the phonon flux and the vibrational mismatch between the materials are each subject to the interfacial bond strength. These results demonstrate plasma-based functionalization of graphene surfaces is a viable approach to manipulate the thermal boundary conductance.

Graphene As a Tunnel Barrier: Graphene-Based Magnetic Tunnel Junctions

Graphene has been widely studied for its high in-plane charge carrier mobility and long spin diffusion lengths. In contrast, the out-of-plane charge and spin transport behavior of this atomically thin material have not been well addressed. We show here that while graphene exhibits metallic conductivity in-plane, it serves effectively as an insulator for transport perpendicular to the plane. We report fabrication of tunnel junctions using single-layer graphene between two ferromagnetic metal layers in a fully scalable photolithographic process. The transport occurs by quantum tunneling perpendicular to the graphene plane and preserves a net spin polarization of the current from the contact so that the structures exhibit tunneling magnetoresistance to 425 K. These results demonstrate that graphene can function as an effective tunnel barrier for both charge and spin-based devices and enable realization of more complex graphene-based devices for highly functional nanoscale circuits, such as tunnel transistors, nonvolatile magnetic memory, and reprogrammable spin logic.

High-quality uniform dry transfer of graphene to polymers.

In this paper we demonstrate high-quality, uniform dry transfer of graphene grown by chemical vapor deposition on copper foil to polystyrene. The dry transfer exploits an azide linker molecule to establish a covalent bond to graphene and to generate greater graphene-polymer adhesion compared to that of the graphene-metal foil. Thus, this transfer approach provides a novel alternative route for graphene transfer, which allows for the metal foils to be reused.

Low-resistance spin injection into silicon using graphene tunnel barriers

Spin manipulation in a semiconductor offers a new paradigm for device operation beyond Moores law. Ferromagnetic metals are ideal contacts for spin injection and detection, but the intervening tunnel barrier required to accommodate the large difference in conductivity introduces defects, trapped charge and material interdiffusion, which severely compromise performance. Here, we show that single-layer graphene successfully circumvents the classic issue of conductivity mismatch between a metal and a semiconductor for electrical spin injection and detection, providing a highly uniform, chemically inert and thermally robust tunnel barrier. We demonstrate electrical generation and detection of spin accumulation in silicon above room temperature, and show that the contact resistance-area products are two to three orders of magnitude lower than those achieved with oxide tunnel barriers on silicon substrates with identical doping levels. Our results identify a new route to low resistance-area product spin-polarized contacts, a key requirement for semiconductor spintronic devices that rely on two-terminal magnetoresistance, including spin-based transistors, logic and memory.

Quantifying pulsed laser induced damage to graphene

As an emerging optical material, graphene’s ultrafast dynamics are often probed using pulsed lasers yet the region in which optical damage takes place is largely uncharted. Here, femtosecond laser pulses induced localized damage in single-layer graphene on sapphire. Raman spatial mapping, SEM, and AFM microscopy quantified the damage. The resulting size of the damaged area has a linear correlation with the optical fluence. These results demonstrate local modification of sp2-carbon bonding structures with optical pulse fluences as low as 14 mJ/cm2, an order-of-magnitude lower than measured and theoretical ablation thresholds.

Chemical stability of graphene fluoride produced by exposure to XeF2.

Fluorination can alter the electronic properties of graphene and activate sites for subsequent chemistry. Here, we show that graphene fluorination depends on several variables, including XeF2 exposure and the choice of substrate. After fluorination, fluorine content declines by 50-80% over several days before stabilizing. While highly fluorinated samples remain insulating, mildly fluorinated samples regain some conductivity over this period. Finally, this loss does not reduce reactivity with alkylamines, suggesting that only nonvolatile fluorine participates in these reactions.

Shear Modulus of Monolayer Graphene Prepared by Chemical Vapor Deposition

We report shear modulus (G) and internal friction (Q(-1)) measurements of large-area monolayer graphene films grown by chemical vapor deposition on copper foil and transferred onto high-Q silicon mechanical oscillators. The shear modulus, extracted from a resonance frequency shift at 0.4 K where the apparatus is most sensitive, averages 280 GPa. This is five times larger than those of the multilayered graphene-based films measured previously. The internal friction is unmeasurable within the sensitivity of our experiment and thus bounded above by Q(-1) ≤ 3 × 10(-5), which is orders-of-magnitude smaller than that of multilayered graphene-based films. Neither annealing nor interface modification has a measurable effect on G or Q(-1). Our results on G are consistent with recent theoretical evaluations and simulations carried out in this work, showing that the shear restoring force transitions from interlayer to intralayer interactions as the film thickness approaches one monolayer.

Fluorination of Graphene Enhances Friction Due to Increased Corrugation

The addition of a single sheet of carbon atoms in the form of graphene can drastically alter friction between a nanoscale probe tip and a surface. Here, for the first time we show that friction can be altered over a wide range by fluorination. Specifically, the friction force between silicon atomic force microscopy tips and monolayer fluorinated graphene can range from 5-9 times higher than for graphene. While consistent with previous reports, the combined interpretation from our experiments and molecular dynamics simulations allows us to propose a novel mechanism: that the dramatic friction enhancement results from increased corrugation of the interfacial potential due to the strong local charge concentrated at fluorine sites, consistent with the Prandtl-Tomlinson model. The monotonic increase of friction with fluorination in experiments also demonstrates that friction force measurements provide a sensitive local probe of the degree of fluorination. Additionally, we found a transition from ordered to disordered atomic stick-slip upon fluorination, suggesting that fluorination proceeds in a spatially random manner.

High-Density Amine-Terminated Monolayers Formed on Fluorinated CVD-Grown Graphene

There has been considerable interest in chemically functionalizing graphene films to control their electronic properties, to enhance their binding to other molecules for sensing, and to strengthen their interfaces with matrices in a composite material. Most reports to date have largely focused on noncovalent methods or the use of graphene oxide. Here, we present a method to activate CVD-grown graphene sheets using fluorination followed by reaction with ethylenediamine (EDA) to form covalent bonds. Reacted graphene was characterized via X-ray photoelectron spectroscopy (XPS), attenuated total reflectance Fourier transform infrared spectroscopy (ATR-FTIR), and Raman spectroscopy as well as measurements of electrical properties. The functionalization results in stable, densely packed layers, and the unbound amine of EDA was shown to be active toward subsequent chemical reactions.