Scott G. Walton

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.

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.

The functionalization of graphene using electron-beam generated plasmas

A plasmas-based, reversible functionalization of graphene is discussed. Using electron-beam produced plasmas, oxygen and fluorine functionalities have been added by changing the processing gas mixtures from Ar/O2 to Ar/SF6, respectively. The reversibility of the functionalization was investigated by annealing the samples. The chemical composition and structural changes were studied by x-ray photoelectron spectroscopy and Raman spectroscopy.

Surface composition, chemistry, and structure of polystyrene modified by electron-beam-generated plasma.

Polystyrene (PS) surfaces were treated by electron-beam-generated plasmas in argon/oxygen, argon/nitrogen, and argon/sulfur hexafluoride environments. The resulting modifications of the polymer surface energy, morphology, and chemical composition were analyzed by a suite of complementary analytical techniques: contact angle goniometry, atomic force microscopy (AFM), X-ray photoelectron spectroscopy (XPS), and reflection electron energy loss spectroscopy (REELS). The plasma treatments produced only minimal increases in the surface roughness while introducing the expected chemical modifications: oxygen-based after Ar/O(2) plasma, oxygen- and nitrogen-based after Ar/N(2) plasma, and fluorine-based after Ar/SF(6) plasma. Fluorinated PS surfaces became hydrophobic and did not significantly change their properties over time. In contrast, polymer treated in Ar/O(2) and Ar/N(2) plasmas initially became hydrophilic but underwent hydrophobic recovery after 28 days of aging. The aromatic carbon chemistry in the top 1 nm of these aged surfaces clearly indicated that the hydrophobic recovery was produced by reorientation/diffusion of undamaged aromatic polymer fragments from the bulk rather than by contamination. Nondestructive depth profiles of aged plasma-treated PS films were reconstructed from parallel angle-resolved XPS (ARXPS) measurements using a maximum-entropy algorithm. The salient features of reconstructed profiles were confirmed by sputter profiles obtained with 200 eV Ar ions. Both types of depth profiles showed that the electron-beam-generated plasma modifications are confined to the topmost 3-4 nm of the polymer surface, while valence band measurements and unsaturated carbon signatures in ARXPS and REELS data indicated that much of the PS structure was preserved below 9 nm.

Aminated graphene for DNA attachment produced via plasma functionalization

We demonstrate the use of a unique plasma source to controllably functionalize graphene with nitrogen and primary amines, thereby tuning the chemical, structural, and electrical properties. Critically, even highly aminated graphene remains electronically conductive, making it an ideal transduction material for biosensing. Proof-of-concept testing of aminated graphene as a bio-attachment platform in a biologically active field-effect transistor used for DNA detection is demonstrated.

Plasma-Based Surface Modification of Polystyrene Microtiter Plates for Covalent Immobilization of Biomolecules

In recent years, polymer surfaces have become increasingly popular for biomolecule attachment because of their relatively low cost and desirable bulk physicochemical characteristics. However, the chemical inertness of some polymer surfaces poses an obstacle to more expansive implementation of polymer materials in bioanalytical applications. We describe use of argon plasma to generate reactive hydroxyl moieties at the surface of polystyrene microtiter plates. The plates are then selectively functionalized with silanes and cross-linkers suitable for the covalent immobilization of biomolecules. This plasma-based method for microtiter plate functionalization was evaluated after each step by X-ray photoelectron spectroscopy, water contact angle analysis, atomic force microscopy, and bioimmobilization efficacy. We further demonstrate that the plasma treatment followed by silane derivatization supports direct, covalent immobilization of biomolecules on microtiter plates and thus overcomes challenging issues typically associated with simple physisorption. Importantly, biomolecules covalently immobilized onto microtiter plates using this plasma-based method retained functionality and demonstrated attachment efficiency comparable to commercial preactivated microtiter plates.

Direct mechanochemical cleavage of functional groups from graphene

Mechanical stress can drive chemical reactions and is unique in that the reaction product can depend on both the magnitude and the direction of the applied force. Indeed, this directionality can drive chemical reactions impossible through conventional means. However, unlike heat- or pressure-driven reactions, mechanical stress is rarely applied isometrically, obscuring how mechanical inputs relate to the force applied to the bond. Here we report an atomic force microscope technique that can measure mechanically induced bond scission on graphene in real time with sensitivity to atomic-scale interactions. Quantitative measurements of the stress-driven reaction dynamics show that the reaction rate depends both on the bond being broken and on the tip material. Oxygen cleaves from graphene more readily than fluorine, which in turn cleaves more readily than hydrogen. The technique may be extended to study the mechanochemistry of any arbitrary combination of tip material, chemical group and substrate.

Experimental and theoretical evaluations of electron temperature in continuous electron beam generated plasmas

In this paper an experimental and theoretical evaluation of electron temperature in continuous, electron beam generated plasmas is presented. Spatial distributions of electron temperature and plasma density in pure and diluted argon were measured. The dependence of the electron temperature and plasma density on pressure, gas composition, hollow cathode voltage and magnetic field was investigated as well. It was observed that the electron temperature in argon was less than 1 eV and that a small addition of nitrogen reduced the electron temperature even more. The magnetic field, pressure and beam current did not strongly affect the electron temperature but greatly influenced the plasma density. The experimental findings are supported by analytical estimations of electron temperature in both noble and molecular gases.

Beam-generated plasmas for processing applications

The use of moderate energy electron beams (e-beams) to generate plasma can provide greater control and larger area than existing techniques for processing applications. Kilovolt energy electrons have the ability to efficiently ionize low pressure neutral gas nearly independent of composition. This results in a low-temperature, high-density plasma of nearly controllable composition generated in the beam channel. By confining the electron beam magnetically the plasma generation region can be designated independent of surrounding structures. Particle fluxes to surfaces can then be controlled by the beam and gas parameters, system geometry, and the externally applied rf bias. The Large Area Plasma Processing System (LAPPS) utilizes a 1–5 kV, 2–10 mA/cm2 sheet beam of electrons to generate a 1011–1012 cm−3 density, 1 eV electron temperature plasma. Plasma sheets of up to 60×60 cm2 area have been generated in a variety of molecular and atomic gases using both pulsed and cw e-beam sources. The theoretical basis ...

Epitaxial Growth of III–Nitride/Graphene Heterostructures for Electronic Devices

Epitaxial GaN films were grown by metal organic chemical vapor deposition (MOCVD) on functionalized epitaxial graphene (EG) using a thin (~11 nm) conformal AlN nucleation layer. Raman measurements show a graphene 2D peak at 2719 cm-1 after GaN growth. X-ray diffraction analysis reveals [0001]-oriented hexagonal GaN with (0002) peak rocking curve full width at the half maximum (FWHM) of 544 arcsec. The FWHM values are similar to reported values for GaN grown by MOCVD on sapphire. The GaN layer has a strong room-temperature photoluminescence band edge emission. Successful demonstration of GaN growth on EG opens up the possibility of III–nitride/graphene heterostructure-based electronic devices and promises improved performance.