Nanoscale characterization of graphene and polymer blends using tip-enhanced Raman spectroscopy and 3D surface-enhanced Raman spectroscopy

関西学院大

The emergence of quantum capacitance in epitaxial graphene

We found an intrinsic redistribution of charge arises between epitaxial graphene, which has intrinsically n-type doping, and an undoped substrate. In particular, we studied in detail epitaxial graphene layers thermally elaborated on C-terminated $4H$-$SiC$ ($4H$-$SiC$ ($000{\bar{1}}$)). We have investigated the charge distribution in graphene-substrate systems using Raman spectroscopy. The influence of the substrate plasmons on the longitudinal optical phonons of the $SiC$ substrates has been detected. The associated charge redistribution reveals the formation of a capacitance between the graphene and the substrate. Thus, we give for the first time direct evidence that the excess negative charge in epitaxial monolayer graphene could be self-compensated by the $SiC$ substrate without initial doping. This induced a previously unseen redistribution of the charge-carrier density at the substrate-graphene interface. There a quantum capacitor appears, without resorting to any intentional external doping, as is fundamentally required for epitaxial graphene. Although we have determined the electric field existing inside the capacitor and revealed the presence of a minigap ($\approx 4.3meV$) for epitaxial graphene on $4H$-$SiC$ face terminated carbon, it remains small in comparison to that obtained for graphene on face terminated $Si$. The fundamental electronic properties found here in graphene on $SiC$ substrates may be important for developing the next generation of quantum technologies and electronic/plasmonic devices.Comment: 26 pages, 8 figures, available online as uncorrected proof, Journal of Materials Chemistry C (2016

Synthesis of Quasi-Freestanding Graphene Films Using Radical Species Formed in Cold Plasmas

For over a decade, the Stinespring laboratory has investigated scalable, plasma assisted synthesis (PAS) methods for the growth of graphene films on silicon carbide (SiC). These typically utilized CF4-based inductively coupled plasma (ICP) with reactive ion etching (RIE) to selectively etch silicon from the SiC lattice. This yielded a halogenated carbon-rich surface layer which was then annealed to produce the graphene layers. The thickness of the films was controlled by the plasma parameters, and overall, the process was readily scalable to the diameter of the SiC wafer. The PAS process reproducibly yielded two- to three-layer thick graphene films that were highly tethered to the underlying SiC substrate via an intermediate buffer layer. The buffer layer was compositionally similar to graphene. However, a significant number of graphene carbons were covalently bound to silicon atoms in the underlying substrate. This tethering lead to mixing of the film and substrate energy bands which degraded many of graphene’s most desirable electrical properties. The research described in this dissertation was aimed at improving graphene quality by reducing the extent of tethering using a fundamentally different plasma etching mechanism while maintaining scalability. In the ICP-RIE process, the etchant species include F and CFx (x = 1-3) radicals and their corresponding positive ions. These radicals are classified as “cold plasma species” in the sense that they are nominally in thermal equilibrium with the substrate and walls of the system. In contrast, the electrons exist at extremely high temperature (energy), and the ionic species are accelerated to energies on the order of several hundred electron volts by the plasma bias voltage that exists between the plasma and substrate. As a result, the ionic species create a directional, high rate etch that is dominated by physical etching characterized by energy and momentum transfer. In contrast, the neutral radicals chemically etch the surface at a much lower rate. In this work, the effects of physical etching due to high energy ions were eliminated by shielding the SiC substrate using a mask (e.g., quartz) supported by silicon posts. In this way, a microplasma consisting of chemically reactive cold plasma species was created in the small space between the substrate surface and the backside of the quartz mask. This process, referred to here as microplasma assisted synthesis (MPAS), was used to produce graphene films. A parametric investigation was conducted to determine the influence of MPAS operating parameters on graphene quality. The key parameters investigated included ICP power, RIE power, etch time, various mask materials, microreactor height, substrate cooling, initial surface morphology and SiC polytype. The resulting graphene films were characterized by x-ray photoelectron spectroscopy (XPS), Raman spectroscopy, and atomic force microscopy (AFM). Following optimization of the MPAS process, some tethering of the graphene films remained. However, films produced by MPAS consistently exhibited significantly less tethering than those produced using the PAS process. Moreover, both XPS and Raman spectroscopy indicated that these films were quasi-free standing, and, in some cases, they approached free standing graphene. From a wide view, the results of these studies demonstrate the potential of MPAS as a technique for realizing the controlled synthesis of high-quality, lightly tethered mono-, and few-layer graphene films directly on an insulating substrate. On a more fundamental level, the results of these studies provide insight into the surface chemistry of radical species

Growth of Thin Oxidation-Resistive Crystalline Si Nanostructures on Graphene

We report the growth of Si nanostructures, either as thin films or nanoparticles, on graphene substrates. The Si nanostructures are shown to be single crystalline, air stable and oxidation resistive, as indicated by the observation of a single crystalline Si Raman mode at around 520 cm-1, a STM image of an ordered surface structure under ambient condition, and a Schottky junction with graphite. Ultra-thin silicon regions exhibit silicene-like behavior, including a Raman mode at around 550 cm-1, a triangular lattice structure in STM that has distinctly different lattice spacing from that of either graphene or thicker Si, and metallic conductivity of up to 500 times higher than that of graphite. This work suggests a bottom-up approach to forming a Si nanostructure array on a large scale patterned graphene substrate for fabricating nanoscale Si electronic devices

Fundamentals and Recent Advances in Epitaxial Graphene on SiC

This book is a compilation of recent studies by recognized experts in the field of epitaxial graphene working towards a deep comprehension of growth mechanisms, property engineering, and device processing. The results of investigations published within this book develop cumulative knowledge on matters related to device-quality epaxial graphene on SiC, bringing this material closer to realistic applications